TWI414543B - Fiber reinforced thermoplastic resin molded body, molding material, and process for manufacturing the same - Google Patents

Fiber reinforced thermoplastic resin molded body, molding material, and process for manufacturing the same Download PDF

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Publication number
TWI414543B
TWI414543B TW96106295A TW96106295A TWI414543B TW I414543 B TWI414543 B TW I414543B TW 96106295 A TW96106295 A TW 96106295A TW 96106295 A TW96106295 A TW 96106295A TW I414543 B TWI414543 B TW I414543B
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fiber
thermoplastic resin
resin molded
reinforced thermoplastic
molding material
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TW96106295A
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Chinese (zh)
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TW200736306A (en
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Shoji Murai
Masato Honma
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Toray Industries
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/465—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating by melting a solid material, e.g. sheets, powders of fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2303/00—Use of resin-bonded materials as reinforcement
    • B29K2303/04—Inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2503/00—Use of resin-bonded materials as filler
    • B29K2503/04—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel
    • Y10T428/249945—Carbon or carbonaceous fiber

Abstract

According to the present invention, a fiber-reinforced thermoplastic resin molded article in which monofilamentous carbon fibers are contained in a thermoplastic resin in a high content, such fibers having long fiber lengths and being randomly arranged, is provided. Also, a molding material comprising monofilamentous carbon fibers and monofilamentous thermoplastic resin fibers, in which the carbon fibers are contained in a high content, such fibers having long fiber lengths and being randomly arranged, is provided. In addition, a method for producing a fiber-reinforced thermoplastic resin molded article, comprising molding the molding material by compression molding, is provided.

Description

纖維強化熱可塑性樹脂成形體、成形材料及其製法Fiber-reinforced thermoplastic resin molded body, forming material and preparation method thereof

本發明關於纖維強化熱可塑性樹脂成形體、成形材料及其製法。本發明的纖維強化熱可塑性樹脂成形體，由於以高含有率含有單纖維狀的碳纖維，其纖維長度長，而且碳纖維被任意地配置，故力學特性及其各向同性優異，適用於電氣．電子機器、土木．建築、汽車、航空器的零件、構造零件及殼體等。本發明的成形材料由於係由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，故操作性優良，而且由於以高含有率含有碳纖維，其纖維長度長，且碳纖維被任意地配置，故可適用於力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體之成形。本發明的製法係為用上述成形材料的壓縮成形法，適用於製造力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體。The present invention relates to a fiber-reinforced thermoplastic resin molded body, a molding material, and a process for producing the same. The fiber-reinforced thermoplastic resin molded article of the present invention contains a single-fiber carbon fiber at a high content, has a long fiber length, and has carbon fibers arbitrarily disposed. Therefore, it is excellent in mechanical properties and isotropy, and is suitable for electrical use. Electronic machines, civil engineering. Construction, automotive, aircraft parts, structural parts and housings. Since the molding material of the present invention is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber, it has excellent handleability, and since it contains carbon fibers at a high content rate, the fiber length is long and the carbon fibers are arbitrarily disposed. Therefore, it can be applied to the formation of a fiber-reinforced thermoplastic resin molded body excellent in mechanical properties and isotropy. The production method of the present invention is a compression molding method using the above-mentioned molding material, and is suitable for producing a fiber-reinforced thermoplastic resin molded article excellent in mechanical properties and isotropy.

由碳纖維和熱可塑性樹脂所構成的纖維強化熱可塑性樹脂成形體，由於比強度、比剛性優異，故廣用於電氣．電子用途、土木．建築用途、汽車用途、航空器用途等。A fiber-reinforced thermoplastic resin molded body composed of carbon fiber and thermoplastic resin is widely used for electrical applications because of its excellent specific strength and specific rigidity. Electronic use, civil engineering. Building use, automotive use, aircraft use, etc.

一般而言，纖維強化熱可塑性樹脂成形體，為了提高力學特性高，有以連續纖維來使用碳纖維。但另一方面，有賦形性差、複雜形狀的纖維強化熱可塑性樹脂成形體之製造困難的情況。因此，藉由使碳纖維成為不連續纖維，則可適用於製造複雜形狀的纖維強化熱可塑性樹脂成形體。In general, in the fiber-reinforced thermoplastic resin molded body, in order to improve the mechanical properties, carbon fibers are used as continuous fibers. On the other hand, however, it is difficult to manufacture a fiber-reinforced thermoplastic resin molded article having a poor formability and a complicated shape. Therefore, by making carbon fibers into discontinuous fibers, it is suitable for producing a fiber-reinforced thermoplastic resin molded body having a complicated shape.

例如，以提高此等纖維強化熱可塑性樹脂成形體的力學特性及其各向同性為手段，有提案將在熱可塑性樹脂中含浸有束狀碳纖維的長方形片，配置於任意方向而成的纖維強化熱可塑性樹脂成形體(參照日本發明專利第2507565號公報(第4頁、第18行))。然而，由於纖維強化熱可塑性樹脂成形體中的碳纖維係以成束狀態存在著，故在碳纖維的束與束之間隙中發生僅由樹脂所構成的富樹脂部，而有降低力學特性的情況。For example, in order to improve the mechanical properties and isotropy of these fiber-reinforced thermoplastic resin molded bodies, a rectangular sheet in which a bundle of carbon fibers is impregnated into a thermoplastic resin and disposed in any direction is proposed. A thermoplastic resin molded body (refer to Japanese Patent No. 2507565 (page 4, line 18)). However, since the carbon fibers in the fiber-reinforced thermoplastic resin molded body are present in a bundled state, a resin-rich portion composed only of a resin is generated in the gap between the bundle of the carbon fibers and the bundle, and the mechanical properties are lowered.

又，有提案將由被集束的不連續碳纖維與熱可塑性樹脂纖維所成的可冲壓片壓縮成形而得的熱可塑性樹脂成形體(參照特開2002－212311號公報(第2頁、第21行))。然而，由於熱可塑性樹脂的熔融黏度高，故熱可塑性樹脂不能含浸到所集束的碳纖維束內，而成為未含浸部，有降低力學特性的情況。In addition, a thermoplastic resin molded body obtained by compression-molding a stampable sheet of a bundle of discontinuous carbon fibers and a thermoplastic resin fiber is proposed (see JP-A-2002-212311 (page 2, line 21). ). However, since the thermoplastic resin has a high melt viscosity, the thermoplastic resin cannot be impregnated into the bundle of carbon fibers, and becomes an unimpregnated portion, which may lower the mechanical properties.

因此，有提案將由單纖維狀的不連續碳纖維與熱可塑性樹脂粉體所構成的碳纖維的體積含有率高之成形材料，壓縮成形而得的熱可塑性樹脂成形體(參照日本發明專利第1761874號公報(第1頁、第2行))。然而，由不連續強化纖維與熱可塑性樹脂粒子所成的成形材料，在成形材料的製造程序中，尤其在成形材料的移送程序中，以及在纖維強化熱可塑性樹脂成形體的製造程序中，尤其在處理成形材料的輸送程序中，由於熱可塑性樹脂粒子從成形材料脫落，故作成形材料有操作性差的問題。Therefore, there is a proposal of a thermoplastic resin molded body obtained by compression-molding a molding material having a high volume fraction of carbon fibers composed of a single-fiber discontinuous carbon fiber and a thermoplastic resin powder (refer to Japanese Patent No. 1761874) (Page 1, line 2)). However, the molding material formed by the discontinuous reinforcing fibers and the thermoplastic resin particles is particularly useful in the manufacturing process of the molding material, particularly in the transfer process of the molding material, and in the manufacturing process of the fiber-reinforced thermoplastic resin molded body. In the transporting process for processing the molding material, since the thermoplastic resin particles are detached from the molding material, the molding material has a problem of poor workability.

又，有提案將由均勻分散的碳纖維與熱可塑性樹脂所得到的纖維強化樹脂片材料加熱成形而得的力學特性高之纖維強化熱可塑性樹脂成形體(參照特開平6－99431號公報(第2頁、第50行))。然而，由於在將纖維強化樹脂片材料加熱成形的程序中，纖維強化樹脂片材料會流動，而使碳纖維在流動方向中配向，有損害力學特性的各向同性之情況。In addition, a fiber-reinforced thermoplastic resin molded article having a high mechanical property obtained by heat-molding a fiber-reinforced resin sheet material obtained by uniformly dispersing carbon fibers and a thermoplastic resin is proposed (see Japanese Patent Publication No. 6-99431 (Page 2) , line 50)). However, in the process of heat-forming the fiber-reinforced resin sheet material, the fiber-reinforced resin sheet material flows, and the carbon fibers are aligned in the flow direction, which impairs the isotropy of the mechanical properties.

本發明鑒於相關先前技術的背景，目的為提供力學特性及其各向同性經提高的纖維強化熱可塑性樹脂成形體，其藉由在熱可塑性樹脂中以高含有率含有單纖維狀的碳纖維，該碳纖維的纖維長度長，而且任意地配置碳纖維。The present invention has been made in view of the background of the related art, and an object thereof is to provide a fiber-reinforced thermoplastic resin molded article having improved mechanical properties and isotropy thereof, which comprises a single-fiber carbon fiber at a high content in a thermoplastic resin. The carbon fiber has a long fiber length and is arbitrarily disposed with carbon fibers.

本發明鑒於相關先前技術的背景，目的為提供可適用於力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體之成形材料，其由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，而提高操作性，而且以高含有率含有碳纖維，該纖維長度長，且碳纖維被任意地配置。The present invention has been made in view of the background of the related art, and an object of the invention is to provide a molding material for a fiber-reinforced thermoplastic resin molded article which is excellent in mechanical properties and isotropy, which is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin. The fibers are composed of fibers to improve workability, and contain carbon fibers at a high content rate, the fibers have a long length, and the carbon fibers are arbitrarily disposed.

本發明鑒於相關先前技術的背景，目的為提供藉由將上述成形材料壓縮成形，以製造力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體之方法。The present invention has been made in view of the background of the related art, and an object of the invention is to provide a method for producing a fiber-reinforced thermoplastic resin molded article excellent in mechanical properties and isotropy by compression-molding the above-mentioned molding material.

本發明為了達成上述目的，採用以下的構成。In order to achieve the above object, the present invention adopts the following constitution.

(1)一種纖維強化熱可塑性樹脂成形體，其係由20~65重量%的熱可塑性樹脂與35~80重量%的碳纖維所成的成形體，該碳纖維係單纖維狀，而且該碳纖維的重量平均纖維長度(Lw)係在0.5~10mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在－0.25~0.25的範圍。(1) A fiber-reinforced thermoplastic resin molded article comprising a molded body of 20 to 65% by weight of a thermoplastic resin and 35 to 80% by weight of carbon fibers, wherein the carbon fibers are monofilament-shaped, and the weight of the carbon fibers The average fiber length (Lw) is in the range of 0.5 to 10 mm, and the orientation parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25.

(2)如上述(1)中記載的纖維強化熱可塑性樹脂成形體，其中上述碳纖維之本說明書中所定義的分散參數係在0~25%的範圍。(2) The fiber-reinforced thermoplastic resin molded article according to the above (1), wherein the dispersion parameter defined in the specification of the carbon fiber is in the range of 0 to 25%.

(3)如上述(1)或(2)中記載的纖維強化熱可塑性樹脂成形體，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最大值係0.29以下。(3) The fiber-reinforced thermoplastic resin molded article according to the above (1) or (2), wherein, in the distribution angle degree distribution of the carbon fiber, the maximum degree of the relative degree of the 30° mark defined in the present specification It is 0.29 or less.

(4)如上述(1)~(3)中任一項記載的纖維強化熱可塑性樹脂成形體，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最小值係0.03以上。(4) The fiber-reinforced thermoplastic resin molded article according to any one of the above-mentioned (1), wherein the relative degree of the 30° mark defined in the present specification in the distribution angle degree distribution of the carbon fiber is The minimum value is 0.03 or more.

(5)如上述(1)~(4)中任一項記載的纖維強化熱可塑性樹脂成形體，其中上述碳纖維的纖維長度1.0mm以上的碳纖維條數係為總碳纖維條數的30~100%之範圍。The fiber-reinforced thermoplastic resin molded article according to any one of the above-mentioned, wherein the carbon fiber has a fiber length of 1.0 mm or more and the number of carbon fibers is 30 to 100% of the total number of carbon fibers. The scope.

(6)如上述(1)~(5)中任一項記載的纖維強化熱可塑性樹脂成形體，其中上述纖維強化熱可塑性樹脂成形體之本說明書中所定義的空隙率係5%以下。The fiber-reinforced thermoplastic resin molded article according to any one of the above aspects, wherein the fiber-reinforced thermoplastic resin molded article has a porosity of 5% or less as defined in the specification.

(7)如上述(1)~(6)中任一項記載的纖維強化熱可塑性樹脂成形體，其中上述纖維強化熱可塑性樹脂成形體之根據ISO178的彎曲強度係在350~1100MPa的範圍。The fiber-reinforced thermoplastic resin molded article according to any one of the above-mentioned, wherein the fiber-reinforced thermoplastic resin molded article has a flexural strength according to ISO178 of 350 to 1100 MPa.

(8)如上述(1)~(7)中任一項記載的纖維強化熱可塑性樹脂成形體，其中於上述纖維強化熱可塑性樹脂成形體之根據ISO178的彎曲強度中，彎曲強度的安定性係10%以下。The fiber-reinforced thermoplastic resin molded article according to any one of the above aspects of the present invention, wherein the flexural strength of the fiber-reinforced thermoplastic resin molded article according to ISO178 is stable. 10% or less.

(9)一種成形材料，其係為由20~65重量%的熱可塑性樹脂纖維與35~80重量%的碳纖維所構成的成形材料，由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，該碳纖維的重量平均纖維長度(Lw)係在1~15mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在－0.25~0.25的範圍。(9) A molding material which is a molding material composed of 20 to 65% by weight of thermoplastic resin fibers and 35 to 80% by weight of carbon fibers, and a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber. The weight average fiber length (Lw) of the carbon fiber is in the range of 1 to 15 mm, and the alignment parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25.

(10)如上述(9)中記載的成形材料，其中上述單纖維狀的熱可塑性樹脂纖維係與至少2條以上的上述單纖維狀的碳纖維相接。(10) The molding material according to the above (9), wherein the single-fiber thermoplastic resin fiber is in contact with at least two or more of the above-mentioned single-fiber carbon fibers.

(11)如上述(9)或(10)中記載的成形材料，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最大值係0.29以下。(11) The molding material according to the above (9) or (10), wherein, in the distribution angle degree distribution of the carbon fibers, the maximum value of the relative degree of the 30° embossing defined in the present specification is 0.29 or less.

(12)如上述(9)~(11)中任一項記載的成形材料，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最小值係0.03以上。(12) The molding material according to any one of the above-mentioned (9), wherein, in the distribution angle degree distribution of the carbon fiber, the minimum degree of the relative degree of the 30° engraving defined in the present specification is 0.03. the above.

(13)如上述(9)~(12)中任一項記載的成形材料，其中上述碳纖維之本說明書中所定義的分散參數係在0~25%的範圍。(13) The molding material according to any one of the above-mentioned (9), wherein the carbon fiber has a dispersion parameter defined in the specification of 0 to 25%.

(14)如上述(9)~(13)中任一項記載的成形材料，其中上述碳纖維的重量平均纖維長度(Lw)與數平均纖維長度(Ln)的比(Lw/Ln)係在1.0~2.5的範圍。The molding material according to any one of the above-mentioned (9), wherein a ratio (Lw/Ln) of the weight average fiber length (Lw) to the number average fiber length (Ln) of the carbon fiber is 1.0. The range of ~2.5.

(15)一種纖維強化熱可塑性樹脂成形體之製法，其係將上述(9)~(14)中任一項記載的成形材料，以含有至少以下(I)~(V)之步驟的壓縮成形法來成形：(I)將成形材料所含有的熱可塑性樹脂加熱熔融之步驟，(Ⅱ)將成形材料配置於模具中之步驟，(Ⅲ)以模具來加壓成形材料之步驟，(Ⅳ)在模具內將成形材料固化之步驟，(V)打開模具，將纖維強化熱可塑性樹脂成形體脫模之步驟。(15) A method of producing a fiber-reinforced thermoplastic resin molded article, wherein the molding material according to any one of the above (9) to (14) is subjected to compression molding comprising at least the following steps (I) to (V) Forming: (I) a step of heating and melting a thermoplastic resin contained in a molding material, (II) a step of disposing a molding material in a mold, and (III) a step of pressing a molding material by a mold, (IV) The step of solidifying the shaped material in the mold, and (V) the step of opening the mold to demold the fiber-reinforced thermoplastic resin molded body.

(16)如上述(15)中記載的纖維強化熱可塑性樹脂成形體之製法，其中於(Ⅲ)的步驟中，進行至少1次以上的去除對成形材料的加壓，再度將成形材料加壓的操作。(16) The method for producing a fiber-reinforced thermoplastic resin molded article according to the above (15), wherein in the step (III), at least one or more removals are performed to pressurize the molding material, and the molding material is again pressurized. Operation.

(17)如上述(15)或(16)中記載的纖維強化熱可塑性樹脂成形體之製法，其中上述壓縮成形的加壓力係2~40MPa。(17) The method for producing a fiber-reinforced thermoplastic resin molded article according to the above (15) or (16), wherein the compression molding pressure is 2 to 40 MPa.

(18)如(15)~(17)中任一項記載的纖維強化熱可塑性樹脂成形體之製法，其中配置於上述模具的模腔內之成形材料的裝料率係80%以上。The method of producing a fiber-reinforced thermoplastic resin molded article according to any one of the aspects of the present invention, wherein the molding material disposed in the cavity of the mold has a charging rate of 80% or more.

本發明的纖維強化熱可塑性樹脂成形體，由於單纖維狀的碳纖維以高含有率含於熱可塑性樹脂中，其纖維長度長，而且碳纖維被任意地配置，故可得到力學特性高、更具有各向同性的力學特性之纖維強化熱可塑性樹脂成形體。該纖維強化熱可塑性樹脂成形體係適用於電氣．電子機器、OA機器、家電機器、土木．建築、汽車、航空器的零件、構造零件及殼體等。In the fiber-reinforced thermoplastic resin molded article of the present invention, since the single-fiber carbon fiber is contained in the thermoplastic resin at a high content, the fiber length is long and the carbon fibers are arbitrarily arranged, so that the mechanical properties are high and each has a higher mechanical property. A fiber-reinforced thermoplastic resin molded body having the same mechanical properties. The fiber reinforced thermoplastic resin molding system is suitable for electrical applications. Electronic equipment, OA machines, home appliances, civil engineering. Construction, automotive, aircraft parts, structural parts and housings.

本發明的成形材料，因為係由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，故操作性優良，而且因為以高含有率含有碳纖維，其纖維長度長，且碳纖維被任意地配置，故能得到可適用於力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體之成形材料。Since the molding material of the present invention is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber, it has excellent handleability, and since it contains carbon fibers at a high content rate, the fiber length is long, and the carbon fibers are arbitrarily According to the arrangement, it is possible to obtain a molding material suitable for a fiber-reinforced thermoplastic resin molded article excellent in mechanical properties and isotropy.

又，藉由將上述成形材料壓縮成形，可製造力學特性高、更具有各向同性的力學特性之纖維強化熱可塑性樹脂成形體。Further, by compression-molding the above-mentioned molding material, it is possible to produce a fiber-reinforced thermoplastic resin molded article having high mechanical properties and more isotropic mechanical properties.

本說明書包括本案優先權之基礎的日本發明專利申請案2006－47987號的說明書及/或圖面中所記載的內容。The present specification includes the contents described in the specification and/or drawings of Japanese Patent Application No. 2006-47987, which is the priority of the present disclosure.

實施發明的最佳形態Best form for implementing the invention

以下更詳細說明本發明的纖維強化熱可塑性樹脂成形體、成形材料及其製法。Hereinafter, the fiber-reinforced thermoplastic resin molded article, the molding material, and the method for producing the same according to the present invention will be described in more detail.

『纖維強化熱可塑性樹脂成形體』"Fiber-reinforced thermoplastic resin molded body"

本發明的纖維強化熱可塑性樹脂成形體係由20~65重量%的熱可塑性樹脂與35~80重量%的碳纖維所成的成形體，該碳纖維係單纖維狀，而且該碳纖維的重量平均纖維長(Lw)係在0.5~10mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在－0.25~0.25的範圍。The fiber-reinforced thermoplastic resin molding system of the present invention comprises a molded body of 20 to 65% by weight of a thermoplastic resin and 35 to 80% by weight of carbon fibers, the carbon fiber being monofibrous, and the carbon fiber having a weight average fiber length ( Lw) is in the range of 0.5 to 10 mm, and the alignment parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25.

本發明的纖維強化熱可塑性樹脂成形體之碳纖維的重量含有率，就相對於纖維強化熱可塑性樹脂成形體而言，係35~80重量%，較佳係38~75重量%，更佳係40~70重量%。碳纖維的重量含有率若低於35重量%，則纖維強化熱可塑性樹脂成形體的力學特性在作為構造零件上會不足。再者，於成形體的成形步驟中，由於成形材料會流動，碳纖維配向於流動方向中，而亦會損害力學特性的各向同性。又，碳纖維的重量含有率若超過80重量%，則對於碳纖維而言的熱可塑性樹脂之量係根本地變少，會顯著降低纖維強化熱可塑性樹脂成形體的力學特性。The weight ratio of the carbon fiber of the fiber-reinforced thermoplastic resin molded article of the present invention is 35 to 80% by weight, preferably 38 to 75% by weight, more preferably 40% by weight based on the fiber-reinforced thermoplastic resin molded article. ~70% by weight. When the weight content of the carbon fiber is less than 35% by weight, the mechanical properties of the fiber-reinforced thermoplastic resin molded article may be insufficient as structural members. Further, in the forming step of the formed body, since the forming material flows, the carbon fibers are aligned in the flow direction, and the isotropy of the mechanical properties is also impaired. In addition, when the weight content of the carbon fiber exceeds 80% by weight, the amount of the thermoplastic resin for the carbon fiber is substantially reduced, and the mechanical properties of the fiber-reinforced thermoplastic resin molded article are remarkably lowered.

本發明的纖維強化熱可塑性樹脂成形體之碳纖維係單纖維狀。此處，所謂的單纖維狀，係如第1圖所示地，於纖維強化熱可塑性樹脂成形體的剖面中，碳纖維顯示實質均勻分散的狀態。如第2圖所示地，於纖維強化熱可塑性樹脂成形體的剖面中，碳纖維若以束狀態存在，則在碳纖維之束與束的間隙中發生僅由樹脂所構成的富樹脂部，力學特性會降低。又，碳纖維若以束狀態存在，則熱可塑性樹脂不能含浸到碳纖維束內，成為未含浸部，力學特性亦會降低。The carbon fiber-reinforced thermoplastic resin molded article of the present invention has a carbon fiber-like monofilament. Here, the single fiber shape is a state in which the carbon fibers show a substantially uniform dispersion in the cross section of the fiber-reinforced thermoplastic resin molded body as shown in Fig. 1 . As shown in Fig. 2, in the cross section of the fiber-reinforced thermoplastic resin molded body, when the carbon fibers are present in a bundle state, a resin-rich portion composed of only a resin is formed in the gap between the bundle of carbon fibers and the bundle, and the mechanical properties are obtained. Will decrease. Further, when the carbon fibers are present in a bundle state, the thermoplastic resin is not impregnated into the carbon fiber bundles, and is not impregnated, and the mechanical properties are also lowered.

本發明的纖維強化熱可塑性樹脂成形體之碳纖維的重量平均纖維長度(Lw)係0.5~10mm，較佳係0.8~8mm，更佳係1~7mm。碳纖維的重量平均纖維長度(Lw)若低於0.5mm，則作為構造零件的力學特性會不足，而若超過10mm，則碳纖維不能成為單纖維狀，在成形體中會發生空隙，力學特性會降低。The carbon fiber of the fiber-reinforced thermoplastic resin molded article of the present invention has a weight average fiber length (Lw) of 0.5 to 10 mm, preferably 0.8 to 8 mm, more preferably 1 to 7 mm. When the weight average fiber length (Lw) of the carbon fiber is less than 0.5 mm, the mechanical properties of the structural component may be insufficient, and if it exceeds 10 mm, the carbon fiber may not be a single fiber, and voids may occur in the molded body, and mechanical properties may be lowered. .

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的觀點看，碳纖維的數平均纖維長度(Ln)較佳係0.4~9mm，更佳係0.7~7mm，特佳係0.9~6mm。In the fiber-reinforced thermoplastic resin molded article of the present invention, the number average fiber length (Ln) of the carbon fiber is preferably 0.4 to 9 mm, more preferably 0.7 to 7 mm, and particularly preferably 0.9 to 6 mm, from the viewpoint of mechanical properties.

此處，重量平均纖維長度(Lw)及數平均纖維長(Ln)係依照以下方法來測定。從纖維強化熱可塑性樹脂成形體抽出碳纖維，任意地選出400條，以光學顯微鏡或掃描型電子顯微鏡來測定其長度直到1μm單位為止，依照下式，算出其重量平均纖維長度(Lw)及數平均纖維長度(Ln)而進行。Here, the weight average fiber length (Lw) and the number average fiber length (Ln) were measured by the following methods. The carbon fiber was taken out from the fiber-reinforced thermoplastic resin molded body, and 400 pieces were arbitrarily selected, and the length was measured up to 1 μm unit by an optical microscope or a scanning electron microscope, and the weight average fiber length (Lw) and number average were calculated according to the following formula. The fiber length (Ln) is carried out.

．重量平均纖維長度(Lw)＝Σ(Li×Wi/100)．數平均纖維長度(Ln)＝(ΣLi)/400．Li：所測定的纖維長度(i＝1、2、3、．．．、400)．Wi：纖維長度Li的纖維之重量分率(i＝1、2、3、．．．、400). Weight average fiber length (Lw) = Σ (Li × Wi / 100). Number average fiber length (Ln) = (ΣLi) / 400. Li: measured fiber length (i = 1, 2, 3, ..., 400). Wi: weight fraction of fibers of fiber length Li (i = 1, 2, 3, ..., 400)

作為碳纖維的抽出方法，可為切出纖維強化熱可塑性樹脂成形體的一部分，以讓熱可塑性樹脂溶解的溶劑使充分溶解後，藉由過濾等的習知操作可與碳纖維分離。於沒有溶解熱可塑性樹脂的溶劑之情況，可使用切出纖維強化熱可塑性樹脂成形體的一部分，在加熱爐中焚燒去除熱可塑性樹脂，以分離出碳纖維的手法。若任意抽出的測定碳纖維條數為400條以上的話，則所算出的碳纖維之重量平均纖維長度(Lw)及數平均纖維長度(Ln)的值係成為幾乎沒有變化。As a method of extracting the carbon fibers, a part of the fiber-reinforced thermoplastic resin molded body can be cut out, and the solvent in which the thermoplastic resin is dissolved can be sufficiently dissolved, and then separated from the carbon fibers by a conventional operation such as filtration. In the case where the solvent of the thermoplastic resin is not dissolved, a method of cutting out a part of the fiber-reinforced thermoplastic resin molded body and incinerating the thermoplastic resin in a heating furnace to separate the carbon fibers can be used. When the number of the carbon fibers to be extracted is 400 or more, the calculated values of the weight average fiber length (Lw) and the number average fiber length (Ln) of the carbon fibers are almost unchanged.

於本發明的纖維強化熱可塑性樹脂成形體表面中，碳纖維的配向狀態係以配向參數(fp)來表示。本發明中的纖維強化熱可塑性樹脂成形體之配向參數(fp)，係為將自纖維強化熱可塑性樹脂成形體表面起的深度100μm之部分中的碳纖維之纖維配向分布以－1.0~1.0的數值所表示的參數，當fp＝－1.0且fp＝1.0時，係意味碳纖維在1方向中配向，當fp＝0.0時，係意味碳纖維完全任意地配置。於本發明中，若fp在－0.25~0.25的範圍，則纖維強化熱可塑性樹脂成形體表面的碳纖維係實質任意地配置，可充分展現本發明的效果，其較佳係在－0.2~0.2的範圍，更佳係在－0.15~0.15的範圍，特佳係在－0.1~0.1的範圍。若fp低於－0.25，或fp超過0.25，則碳纖維的配向偏差變大，會損害力學特性的各向同性。In the surface of the fiber-reinforced thermoplastic resin molded article of the present invention, the alignment state of the carbon fibers is represented by the alignment parameter (fp). The alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article in the present invention is such that the fibers of the carbon fibers in the portion having a depth of 100 μm from the surface of the fiber-reinforced thermoplastic resin molded article are distributed to a value of -1.0 to 1.0. The parameters indicated, when fp = -1.0 and fp = 1.0, mean that the carbon fibers are aligned in one direction, and when fp = 0.0, it means that the carbon fibers are completely arbitrarily disposed. In the present invention, when fp is in the range of -0.25 to 0.25, the carbon fibers on the surface of the fiber-reinforced thermoplastic resin molded article are substantially arbitrarily disposed, and the effects of the present invention can be sufficiently exhibited, and it is preferably in the range of -0.2 to 0.2. The range is preferably in the range of -0.15 to 0.15, and particularly preferably in the range of -0.1 to 0.1. If fp is lower than -0.25, or fp exceeds 0.25, the misalignment of the carbon fibers becomes large, and the isotropy of the mechanical properties is impaired.

作為配向參數(fp)，聚合物複合物(Polymer Composites)第6冊、第41－46頁(1985)有揭示計測射出成形品截面的纖維配向角度，以算出配向參數的方法。於本發明中，纖維強化熱可塑性樹脂成形體的配向參數(fp)係依照以下方法來測定。切斷纖維強化熱可塑性樹脂成形體的一部分，研磨到自纖維強化熱可塑性樹脂成形體表面起100μm的深度為止，用光學顯微鏡觀察所得到的試驗片，任意地選出400條碳纖維。研磨面的碳纖維一般以橢圓形被確認，以該橢圓的長軸方向當作纖維的配向方向。接著，任意設定成為角度基準的基準直線，測定全部相對於基準直線而言，碳纖維的配向方向所成的角度(以下簡稱配向角度αi)。配向角度αi係測定相對於基準直線而言，反時針旋轉方向的角度，其為0°以上且小於180°的角度。使用該配向角度αi，藉由下式來算出配向參數(fp)。As the alignment parameter (fp), Polymer Composites, Vol. 6, No. 41-46 (1985) discloses a method of measuring the fiber alignment angle of the cross section of the injection molded article to calculate the alignment parameter. In the present invention, the alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article is measured by the following method. A part of the fiber-reinforced thermoplastic resin molded body was cut and polished to a depth of 100 μm from the surface of the fiber-reinforced thermoplastic resin molded body, and the obtained test piece was observed with an optical microscope, and 400 carbon fibers were arbitrarily selected. The carbon fibers of the polished surface are generally confirmed in an elliptical shape, and the long axis direction of the ellipse is regarded as the alignment direction of the fibers. Next, the reference straight line which is the angle reference is arbitrarily set, and the angle formed by the alignment direction of the carbon fibers with respect to the reference straight line (hereinafter referred to as the alignment angle αi) is measured. The alignment angle αi is an angle measured in the counterclockwise direction with respect to the reference straight line, and is an angle of 0° or more and less than 180°. Using the alignment angle αi, the alignment parameter (fp) is calculated by the following equation.

．fp＝2×Σ(cos2αi/400)－1．αi：所測定的配向角度(i＝1、2、3、．．．、400). Fp=2×Σ(cos2αi/400)-1. Ii: measured angle of alignment (i = 1, 2, 3, ..., 400)

若任意選出的碳纖維條數為400條以上，則配向參數(fp)的值係成為幾乎沒有變化。又，若自纖維強化熱可塑性樹脂成形體表面起的深度為在150μm以下的範圍，則配向參數(fp)的值係幾乎沒有變化，可測定纖維強化熱可塑性樹脂成形體表面的配向參數(fp)。作為用於測定纖維強化熱可塑性樹脂成形體的配向參數(fp)之部分，係沒有特別的限制，但較佳為迴避纖維強化熱可塑性樹脂成形體端部，儘可能地使用中央附近之沒有突面、肋條和成形體之厚度變化的部分來進行測定。When the number of arbitrarily selected carbon fibers is 400 or more, the value of the alignment parameter (fp) is almost unchanged. In addition, when the depth from the surface of the fiber-reinforced thermoplastic resin molded article is in the range of 150 μm or less, the value of the alignment parameter (fp) hardly changes, and the alignment parameter of the surface of the fiber-reinforced thermoplastic resin molded article can be measured (fp). ). The portion for determining the alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article is not particularly limited, but it is preferable to avoid the end portion of the fiber-reinforced thermoplastic resin molded body, and to use as much as possible near the center. The surface, the ribs, and the portion of the molded body whose thickness was changed were measured.

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的觀點來看，所含有的碳纖維之分散參數較佳係0~25%，更佳係0~22%，特佳係0~20%。所謂纖維強化熱可塑性樹脂成形體的分散參數，係表示纖維強化熱可塑性樹脂成形體中所含有的碳纖維之重量含有率的變動度之指標，以於本發明中的纖維強化熱可塑性樹脂成形體之剖面中，所測定的碳纖維條數之變動度的值來表示。該分散參數係藉由以下方法來測定。從纖維強化熱可塑性樹脂成形體切出一部分，研磨其剖面，用光學顯微鏡來觀察任意地選出10處的0.1mm×0.1mm之範圍，測定該範圍內所含有的碳纖維之條數。以所選出10處的碳纖維之條數的平均值當作A，以標準偏差當作S，藉由下式來求得分散參數。The fiber-reinforced thermoplastic resin molded article of the present invention preferably has a dispersion parameter of 0 to 25%, more preferably 0 to 22%, and particularly preferably 0 to 20%, from the viewpoint of mechanical properties. The dispersion parameter of the fiber-reinforced thermoplastic resin molded article is an index indicating the degree of change in the weight content of the carbon fiber contained in the fiber-reinforced thermoplastic resin molded article, and is used in the fiber-reinforced thermoplastic resin molded article of the present invention. In the cross section, the value of the degree of change in the number of carbon fibers measured is shown. This dispersion parameter was determined by the following method. A part of the fiber-reinforced thermoplastic resin molded body was cut out, and the cross section was polished, and the range of 0.1 mm × 0.1 mm at 10 places was arbitrarily selected by an optical microscope, and the number of carbon fibers contained in the range was measured. The average value of the number of carbon fibers selected at 10 places was taken as A, and the standard deviation was taken as S, and the dispersion parameter was obtained by the following formula.

．分散參數＝(100×S/A)(單位：%). Dispersion parameter = (100 × S / A) (unit: %)

又，作為用於測定纖維強化熱可塑性樹脂成形體的分散參數之部分，係沒有特別的限制，但較佳為迴避纖維強化熱可塑性樹脂成形體端部，儘可能地使用中央附近之沒有突面、肋條和成形體之厚度變化的部分來進行測定。Moreover, it is not particularly limited as a part for measuring the dispersion parameter of the fiber-reinforced thermoplastic resin molded body, but it is preferable to avoid the end portion of the fiber-reinforced thermoplastic resin molded body, and use no protruding surface near the center as much as possible. The ribs and the portions of the molded body whose thickness is changed are measured.

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的各向同性之觀點來看，碳纖維的配向角度度數分布中，30°刻紋的相對度數之最大值較佳係0.29以下，更佳係0.26以下，特佳係0.23以下。又，本發明的纖維強化熱可塑性樹脂成形體，從力學特性的各向同性之觀點看，碳纖維的配向角度度數分布中，30°刻紋的相對度數之最小值較佳係0.03以上，更佳係0.06以上，特佳係0.10以上。碳纖維的配向角度度數分布中之30°刻紋的相對度數，係表示纖維強化熱可塑性樹脂成形體表面的碳纖維之配向角度分布的指標，於本發明中係將自纖維強化熱可塑性樹脂成形體表面起之深度100μm的部分之碳纖維的配向角度，表示成30°刻紋的相對度數。碳纖維的配向角度度數分布中之30°刻紋的相對度數之最大值和最小值，係藉由以下方法來測定。使用上述配向參數(fp)之算出時所用的400條碳纖維之配向角度αi，製作30°刻紋的碳纖維之配向角度相對度數分布，以其最大值和最小值當作碳纖維的配向角度度數分布中的30°刻紋之相對度數的最大值和最小值。若以任意選出的碳纖維條數為400條以上的話，則碳纖維的配向角度度數分布中的30°刻紋之相對度數的最大值和最小值係成為幾乎沒有變化。又，若係自纖維強化熱可塑性樹脂成形體表面起之深度150μm以下的區域，則碳纖維的配向角度度數分布中之30°刻紋的相對度數之最大值首最小值的變化係幾乎沒有，可測定纖維強化熱可塑性樹脂成形體表面的碳纖維之配向角度分布。又，作為用於測定碳纖維的配向角度度數分布中之30°刻紋的相對度數之最大值和最小值的部分，係沒有特別的限制，但較佳為迴避纖維強化熱可塑性樹脂成形體端部，儘可能地使用中央附近之沒有突面、肋條和成形體之厚度變化的部分來進行測定。碳纖維的配向角度度數分布中的30°刻紋之相對度數的最大值和最小值若為0.17，則意味纖維強化熱可塑性樹脂成形體表面的碳纖維係完全任意地配置。In the fiber-reinforced thermoplastic resin molded article of the present invention, from the viewpoint of isotropy of mechanical properties, in the distribution angle degree distribution of carbon fibers, the maximum value of the relative degree of the 30° engraving is preferably 0.29 or less, more preferably 0.26 or less, particularly preferably 0.23 or less. Further, in the fiber-reinforced thermoplastic resin molded article of the present invention, the minimum value of the relative degree of the 30° embossing is preferably 0.03 or more, more preferably from the viewpoint of isotropy of mechanical properties. It is 0.06 or more, and is particularly preferably 0.10 or more. The relative degree of the 30° mark in the distribution angle degree distribution of the carbon fiber is an index indicating the distribution angle of the carbon fibers on the surface of the fiber-reinforced thermoplastic resin molded body, and is the surface of the fiber-reinforced thermoplastic resin molded body in the present invention. The alignment angle of the carbon fibers of the portion having a depth of 100 μm is expressed as the relative degree of the 30° engraving. The maximum and minimum values of the relative degrees of the 30° scribe in the distribution angle degree distribution of the carbon fibers were determined by the following methods. Using the alignment angle αi of 400 carbon fibers used in the calculation of the above-mentioned alignment parameter (fp), the relative angular distribution of the 30° engraved carbon fibers is made, and the maximum and minimum values are taken as the distribution angle distribution of the carbon fibers. The maximum and minimum values of the relative degrees of the 30° engraving. When the number of arbitrarily selected carbon fibers is 400 or more, the maximum and minimum values of the relative degrees of the 30° scribe in the distribution angle degree distribution of the carbon fibers are hardly changed. In addition, when the surface of the fiber-reinforced thermoplastic resin molded body has a depth of 150 μm or less, the change in the maximum value of the relative degree of the 30° mark in the distribution angle degree distribution of the carbon fiber is almost no change. The alignment angle distribution of the carbon fibers on the surface of the fiber-reinforced thermoplastic resin molded body was measured. Further, the portion for measuring the maximum value and the minimum value of the relative degree of the 30° engraving in the distribution angle degree distribution of the carbon fiber is not particularly limited, but it is preferable to avoid the end portion of the fiber-reinforced thermoplastic resin molded body. As far as possible, the measurement is performed using a portion having no convex surface, ribs, and a thickness change of the molded body near the center. When the maximum value and the minimum value of the relative degree of the 30° mark in the distribution angle degree distribution of the carbon fibers are 0.17, it means that the carbon fibers on the surface of the fiber-reinforced thermoplastic resin molded body are completely arbitrarily disposed.

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的觀點來看，纖維長度為1.0mm以上的碳纖維條數較佳係總碳纖維條數的30~100%，更佳係35~95%，特佳係40~90%。In the fiber-reinforced thermoplastic resin molded article of the present invention, the number of carbon fibers having a fiber length of 1.0 mm or more is preferably from 30 to 100%, more preferably from 35 to 95%, based on the mechanical properties. Tejia is 40~90%.

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的觀點來看，纖維長度為2.0mm以上的碳纖維條數較佳係總碳纖維條數的10~100%，更佳係15~95%，特佳係20~90%。In the fiber-reinforced thermoplastic resin molded article of the present invention, the number of carbon fibers having a fiber length of 2.0 mm or more is preferably from 10 to 100%, more preferably from 15 to 95%, based on the mechanical properties. The special best is 20~90%.

本發明的纖維強化熱可塑性樹脂成形體，從力學特性的觀點來看，纖維長度為3.0mm以上的碳纖維條數較佳係總碳纖維條數的2~100%，更佳係3~95%，特佳係5~90%。In the fiber-reinforced thermoplastic resin molded article of the present invention, the number of carbon fibers having a fiber length of 3.0 mm or more is preferably from 2 to 100%, more preferably from 3 to 95%, based on the mechanical properties. The special system is 5~90%.

本發明的纖維強化熱可塑性樹脂成形體之空隙率，從力學特性的觀點來看，較佳係5%以下，更佳係3%以下，特佳係2%以下。纖維強化熱可塑性樹脂成形體的空隙率，係藉由以下方法來測定。切出纖維強化熱可塑性樹脂成形體的一部分，依照JIS K 7112(1999)之5中所記載的A法(水中置換法)，測定纖維強化熱可塑性樹脂成形體的密度(ρc)。使用該纖維強化熱可塑性樹脂成形體的密度(ρc)及熱可塑性樹脂的密度(ρr)，藉由下式求出纖維強化熱可塑性樹脂成形體的空隙率(Vv)。The porosity of the fiber-reinforced thermoplastic resin molded article of the present invention is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less from the viewpoint of mechanical properties. The void ratio of the fiber-reinforced thermoplastic resin molded article was measured by the following method. A part of the fiber-reinforced thermoplastic resin molded body was cut out, and the density (ρc) of the fiber-reinforced thermoplastic resin molded body was measured in accordance with the A method (aqueous substitution method) described in JIS K 7112 (1999). Using the density (ρc) of the fiber-reinforced thermoplastic resin molded article and the density (ρr) of the thermoplastic resin, the void ratio (Vv) of the fiber-reinforced thermoplastic resin molded article was determined by the following formula.

．Vv＝100－ρc/ρr(單位：體積%). Vv=100-ρc/ρr (unit: vol%)

作為用於測定纖維強化熱可塑性樹脂成形體的空隙率(Vv)之部分，係沒有特別的限制，但較佳為迴避纖維強化熱可塑性樹脂成形體端部，儘可能地使用中央附近之沒有突面、肋條和成形體的厚度變化之部分來進行測定。The portion for measuring the porosity (Vv) of the fiber-reinforced thermoplastic resin molded article is not particularly limited, but it is preferable to avoid the end portion of the fiber-reinforced thermoplastic resin molded body, and to use as much as possible near the center. The surface, the ribs, and the portion of the thickness of the molded body were measured for measurement.

本發明的纖維強化熱可塑性樹脂成形體之根據ISO178所測定的彎曲強度較佳係350~1100MPa，彎曲強度更佳係在370~1000MPa的範圍，特佳係在400~900MPa的範圍。彎曲強度若在較佳的範圍內，則成為當作構造零件可使用的強度之較佳態樣。The flexural strength measured according to ISO178 of the fiber-reinforced thermoplastic resin molded article of the present invention is preferably 350 to 1100 MPa, and the bending strength is preferably in the range of 370 to 1000 MPa, particularly preferably in the range of 400 to 900 MPa. If the bending strength is within a preferred range, it is a preferred aspect of the strength that can be used as a structural part.

又，從力學特性的各向同性之觀點來看，本發明的纖維強化熱可塑性樹脂成形體之根據ISO178所測定的彎曲強度之安定性較佳係10%以下，更佳係8%以下，特佳係7%以下。彎曲強度的安定性之下限值係沒有特別的限定，但從構造零件的各向同性之力學特性的觀點來看，最佳係0%。Moreover, from the viewpoint of the isotropy of the mechanical properties, the stability of the bending strength measured according to ISO 178 of the fiber-reinforced thermoplastic resin molded article of the present invention is preferably 10% or less, more preferably 8% or less. The best is 7% or less. The lower limit of the stability of the bending strength is not particularly limited, but from the viewpoint of the isotropic mechanical properties of the structural part, the optimum is 0%.

再者，本發明的纖維強化熱可塑性樹脂成形體之根據ISO178所測定的彎曲彈性模數，從對構造零件的適用觀點來看，較佳係17GPa以上，更佳係20GPa以上，特佳係23GPa以上。In addition, the flexural modulus of elasticity of the fiber-reinforced thermoplastic resin molded article of the present invention measured according to ISO178 is preferably 17 GPa or more, more preferably 20 GPa or more, and particularly good for 23 GPa from the viewpoint of application of the structural component. the above.

「碳纖維」"carbon fiber"

作為本發明的纖維強化熱可塑性樹脂成形體所用的碳纖維，例如較佳可舉出以聚丙烯腈纖維當作原料的PAN系碳纖維，以煤焦油或石油瀝青當作原料的瀝青系碳纖維，以黏膠嫘縈或醋酸纖維素等當作原料的纖維素系碳纖維，以烴等當作原料的氣相成長系碳纖維，及此等之石墨化纖維等。又，亦可摻合此等2種類以上。其中，特佳為使用強度與彈性模數的平衡優良之PAN系碳纖維。The carbon fiber used for the fiber-reinforced thermoplastic resin molded article of the present invention is preferably, for example, a PAN-based carbon fiber using polyacrylonitrile fiber as a raw material, and a pitch-based carbon fiber using coal tar or petroleum pitch as a raw material. A cellulose-based carbon fiber as a raw material such as a capsule or a cellulose acetate, a vapor-grown carbon fiber using a hydrocarbon or the like as a raw material, and a graphitized fiber or the like. Further, it is also possible to blend two or more of these types. Among them, PAN-based carbon fibers excellent in balance between strength and elastic modulus are particularly preferred.

又，本發明的纖維強化熱可塑性樹脂成形體所用的碳纖維之拉伸強度較佳係3.7GPa以上，更佳係4.0GPa以上，特佳係4.2GPa以上，可減少纖維強化熱可塑性樹脂成形體中的碳纖維之折損。又，該碳纖維的拉伸彈性模數，從對構造零件的適用觀點來看，較佳可使用180~650GPa者。Moreover, the tensile strength of the carbon fiber used for the fiber-reinforced thermoplastic resin molded article of the present invention is preferably 3.7 GPa or more, more preferably 4.0 GPa or more, and particularly preferably 4.2 GPa or more, and the fiber-reinforced thermoplastic resin molded article can be reduced. The carbon fiber is broken. Further, the tensile modulus of the carbon fiber is preferably from 180 to 650 GPa from the viewpoint of application to the structural member.

「熱可塑性樹脂」"thermoplastic resin"

作為本發明的纖維強化熱可塑性樹脂成形體所用的熱可塑性樹脂，例如可舉出從「聚對酞酸乙二酯(PET)、聚對酞酸丁二酯(PBT)、聚對酞酸三亞甲酯(PTT)、聚萘二甲酸乙二酯(PEN)、液晶聚酯等的聚酯，或聚乙烯(PE)、聚丙烯(PP)、聚丁烯等的聚烯烴，或聚氧化甲烯(POM)、聚醯胺(PA)、聚苯硫醚(PPS)、聚酮(PK)、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚腈(PEN)、聚四氟乙烯等的氟系樹脂、液晶聚合物(LCP)」等的結晶性樹脂，「苯乙烯系樹脂、以及聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、聚伸苯醚(PPE)、聚醯亞胺(PI)、聚醯胺醯亞胺(PAI)、聚醚醯亞胺(PEI)、聚碸(PSU)、聚醚碸、聚芳酯(PAR)」等的非晶性樹脂，以及酚系樹脂、苯氧樹脂，另還有聚苯乙烯系、聚烯烴系、聚胺甲酸酯系、聚酯系、聚醯胺系、聚丁二烯系、聚異戊二烯系、氟系、及丙烯腈系等的熱可塑彈性體等，或此等共聚物及改性體等中所選出的熱可塑性樹脂。於本發明中，可採用此等至少1種當作較佳的熱可塑性樹脂。更佳地，從力學特性的觀點來看，聚醯胺(PA)係良好的，從耐熱性的觀點來看，聚苯硫醚(PPS)、聚醚醯亞胺(PEI)、聚醚醚酮(PEEK)係良好的，從經濟性的觀點看，聚丙烯(PP)係良好的。The thermoplastic resin used for the fiber-reinforced thermoplastic resin molded article of the present invention may, for example, be "polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polypyruic acid triamide. Polyester (PTT), polyethylene naphthalate (PEN), polyester such as liquid crystal polyester, or polyolefin such as polyethylene (PE), polypropylene (PP), polybutene, or polyoxylated Alkene (POM), polydecylamine (PA), polyphenylene sulfide (PPS), polyketone (PK), polyether ketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), poly a crystalline resin such as an ether nitrile (PEN), a fluorine-based resin such as polytetrafluoroethylene, or a liquid crystal polymer (LCP), "styrene-based resin, and polycarbonate (PC), polymethyl methacrylate ( PMMA), polyvinyl chloride (PVC), polyphenylene oxide (PPE), polyimine (PI), polyamidimide (PAI), polyetherimide (PEI), polyfluorene (PSU) An amorphous resin such as a polyether oxime or a polyarylate (PAR), a phenol resin or a phenoxy resin, and a polystyrene, a polyolefin, a polyurethane, or a polyester. Polyamide, polybutadiene, polyisoprene, fluorine, and acrylonitrile The thermoplastic resin in a thermoplastic elastomer, copolymers of these or the like and the selected modified. In the present invention, at least one of these may be used as a preferred thermoplastic resin. More preferably, from the viewpoint of mechanical properties, polyamine (PA) is good, and from the viewpoint of heat resistance, polyphenylene sulfide (PPS), polyether quinone imine (PEI), polyether ether The ketone (PEEK) is good, and the polypropylene (PP) is good from the viewpoint of economy.

「添加劑、填充劑等」"Additives, fillers, etc."

於本發明的纖維強化熱可塑性樹脂成形體中，按照其用途而定，更可添加雲母、滑石、高嶺土、矽藻土、膨土、硬矽鈣土、海泡石、綠土、蒙脫石、矽灰石、矽石、碳酸鈣、玻璃珠、玻璃碎片、黏土、二硫化鉬、氧化鈦、氧化鋅、氧化銻、聚磷酸鈣、石墨、硫酸鋇、硫酸鎂、硼酸鋅、硼酸亞鈣、硼酸鋁鬚晶、鈦酸鉀鬚晶及高分子化合物等的填料，金属系、金屬氧化物系、碳黑及石墨粉末等的導電性賦予材，溴化樹脂等的鹵系難燃劑、三氧化銻或五氧化銻等的銻系難燃劑、聚磷酸銨、芳香族磷酸酯及紅磷等的磷系難燃劑、有硼酸金屬鹽、羧酸金屬鹽及芳香族磺醯亞胺金屬鹽等的有機酸金屬鹽系難燃劑、硼酸鋅、鋅、氧化鋅及鋯化合物等的無機系難燃劑、氰尿酸、異氰尿酸、蜜胺、蜜胺氰尿酸酯、蜜胺磷酸酯及氮化胍等的氮系難燃劑、PTFE等的氟系難燃劑、聚有機矽氧烷等的聚矽氧系難燃劑、氫氧化鋁或氫氧化鎂等的金屬氫氧化物系難燃劑、以及其它難燃劑、氧化鎘、氧化鋅、氧化亞銅、氧化銅、氧化亞鐵、氧化鐵、氧化鈷、氧化錳、氧化鉬、氧化錫及氧化鈦等的難燃助劑、顏料、染料、滑劑、脫模劑、相溶化劑、分散劑、雲母、滑石及高嶺土等的結晶核劑、磷酸酯等的可塑劑、熱安定劑、抗氧化劑、防著色劑、紫外線吸收劑、流動性改質劑、發泡劑、抗菌劑、減振劑、防臭劑、滑動性改質劑、及聚醚酯醯胺等的抗靜電劑等。In the fiber-reinforced thermoplastic resin molded article of the present invention, mica, talc, kaolin, diatomaceous earth, bentonite, hard strontium, sepiolite, smectite, montmorillonite may be added depending on the application. , ash stone, vermiculite, calcium carbonate, glass beads, glass shards, clay, molybdenum disulfide, titanium oxide, zinc oxide, cerium oxide, calcium polyphosphate, graphite, barium sulfate, magnesium sulfate, zinc borate, calcium borate a filler such as aluminum borate whisker, potassium titanate whisker and polymer compound, a conductivity imparting material such as a metal system, a metal oxide system, a carbon black or a graphite powder, or a halogen-based flame retardant such as a brominated resin. Antimony-based flame retardant such as antimony trioxide or antimony pentoxide, phosphorus-based flame retardant such as ammonium polyphosphate, aromatic phosphate and red phosphorus, metal borate, metal carboxylate and aromatic sulfonimide An organic acid metal salt such as a metal salt is a flame retardant, an inorganic flame retardant such as zinc borate, zinc, zinc oxide or a zirconium compound, cyanuric acid, isocyanuric acid, melamine, melamine cyanurate or melamine Nitrogen-based flame retardants such as phosphates and tantalum nitride, and fluorine-based flame retardants such as PTFE A polyoxon-based flame retardant such as a polyorganosiloxane or a metal hydroxide-based flame retardant such as aluminum hydroxide or magnesium hydroxide, and other flame retardants, cadmium oxide, zinc oxide, and cuprous oxide. , flame retardant aids such as copper oxide, ferrous oxide, iron oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and titanium oxide, pigments, dyes, slip agents, mold release agents, compatibilizers, dispersants, Crystalline nucleating agents such as mica, talc and kaolin, plasticizers such as phosphate esters, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fluidity modifiers, foaming agents, antibacterial agents, vibration damping agents, Deodorant, slidability modifier, antistatic agent such as polyether ester decylamine, etc.

本發明的纖維強化熱可塑性樹脂成形體、除了使用碳纖維，亦可使用鋁纖維或不銹鋼纖維等的金屬纖維、芳醯胺纖維或PBO纖維等的有機纖維、碳化矽纖維或玻璃纖維等的無機纖維、及麻或洋麻等的天然纖維。特佳為使用玻璃纖維，其在經濟方面係有利的。In the fiber-reinforced thermoplastic resin molded article of the present invention, in addition to carbon fibers, metal fibers such as aluminum fibers or stainless steel fibers, organic fibers such as linaloamide fibers or PBO fibers, inorganic fibers such as lanthanum carbide fibers or glass fibers may be used. , and natural fibers such as hemp or kenaf. It is particularly preferred to use fiberglass, which is economically advantageous.

「用途」"use"

作為本發明的纖維強化熱可塑性樹脂成形體之用途，例如可舉出「個人電腦、顯示器、OA機器、攜帶式電話、攜帶型資訊終端、傳真機、CD、攜帶型MD、攜帶用盒式收錄音機、PDA(電子筆記本等的攜帶資訊終端)、攝影機、數位攝影機、光學機器、音頻器、空調、照明機器、娛樂用品、玩具用品、其它家電製品等的殼體、淺盤、底盤、內裝構件、或其外箱」等的電氣、電子機器零件、「支柱、面板、補強材」等的土木、建材用零件、「各種構件、各種框架、各種鉸鏈、各種扶手、各種車軸、各種車輪用軸承、各種橫樑、傳動軸、輪子、齒輪箱等之懸吊、加速或轉向零件」、「罩、車頂、門、擋泥板、貨車蓋、側板、後端面板、上背面板、前車身、下車紙、各種柱子、各種構件、各種框架、各種橫桿、各種支撐、各種軌道、各種鉸鏈等之外板或車身零件」、「緩衝桿、緩衝桿橫樑、步道、下蓋、引擎蓋、整流板、擾流板、車頸桿、氣動零件等外裝零件」、「儀表板、椅框、門飾、柱飾、方向盤、各種模組等的內裝零件」、或「馬達零件、CNG桶、汽油箱、燃料泵、進氣管、進氣歧管、化油器本體、化油器墊片、各種配管、各種配管等的燃料系、排氣系、或吸氣系零件」等的汽車、二輪車用構造零件、「以及交流終端、交流連接器、IC調整器、調光用電位計、引擎冷卻水接頭、空調用恒溫器基座、暖房溫風流量控制閥、水箱馬達用刷子托架、渦輪機箱、雨刷馬達有關零件、配電器、起動器開關、起動繼電器、洗窗噴嘴、空調面板基板、燃料有關電磁閥用線圈、電池盤、AT托架、前燈支架、踏板外罩、喇叭終端、步進馬達轉子、燈插座、燈反射器、燈罩、剎車活塞、隔噪音板、備用輪胎蓋、電磁點火線圈、機油過濾器、點火裝置箱、車門框板、儀表板」、等的汽車、二輪車用零件、「起落架、翼板、擾流板、邊緣、梯子、升降機、流線條、肋條」等的航空器用零件。從力學特性的觀點來看，較佳為使用於電氣、電子機器用的殼體、土木、建材用的面板、汽車用的構造零件、航空器用的零件。從力學特性及各向同性的觀點來看，特佳為使用於汽車、二輪車用的構造零件。Examples of the use of the fiber-reinforced thermoplastic resin molded article of the present invention include "a personal computer, a display, an OA device, a portable telephone, a portable information terminal, a facsimile machine, a CD, a portable MD, and a portable cassette. Housings, platters, chassis, interiors for recorders, PDAs (portable information terminals such as electronic notebooks), cameras, digital cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment products, toy products, and other home appliances Electrical and electronic equipment parts such as components and their outer casings, and parts for civil engineering and building materials such as "pillars, panels, and reinforcing materials", "various components, various frames, various hinges, various handrails, various axles, and various wheels." Suspension, acceleration or steering parts for bearings, various beams, drive shafts, wheels, gearboxes, etc., "covers, roofs, doors, fenders, truck covers, side panels, rear panels, upper back panels, front body , off-board paper, various columns, various components, various frames, various crossbars, various supports, various tracks, various hinges, etc. , "Buffing rods, bumper beams, trails, lower covers, hoods, rectifying plates, spoilers, neck rods, pneumatic parts and other exterior parts", "dashboard, chair frame, door trim, pillars, steering wheel , internal components such as various modules, or "motor parts, CNG barrels, gasoline tanks, fuel pumps, intake pipes, intake manifolds, carburetor bodies, carburetor gaskets, various piping, various piping "Automobiles and two-wheeled structural components such as fuel systems, exhaust systems, and air intake components", and "AC terminals, AC connectors, IC regulators, dimming potentiometers, engine cooling water joints, and air conditioners." Thermostat base, greenhouse warm air flow control valve, brush motor brush holder, turbine chassis, wiper motor related parts, distributor, starter switch, starter relay, window washing nozzle, air conditioning panel base, fuel-related solenoid valve Coil, battery tray, AT bracket, headlight bracket, pedal cover, speaker terminal, stepper motor rotor, lamp socket, lamp reflector, lampshade, brake piston, noise barrier, spare tire cover, electromagnetic ignition wire Aircraft such as oil filters, ignition boxes, door frame panels, instrument panels, etc., parts for vehicles, two-wheeled vehicles, "landing gear, wings, spoilers, edges, ladders, lifts, flow lines, ribs" Use parts. From the viewpoint of mechanical properties, it is preferably used for housings for electric and electronic equipment, panels for civil engineering, building materials, structural parts for automobiles, and parts for aircraft. From the viewpoint of mechanical properties and isotropy, it is particularly suitable for structural parts used in automobiles and two-wheeled vehicles.

『成形材料』『Forming material』

接著，說明本發明的成形材料。Next, the molding material of the present invention will be described.

本發明的成形材料係為由20~65重量%的熱可塑性樹脂纖維與35~80重量%的碳纖維所構成的成形材料，由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所成，該碳纖維的重量平均纖維長度(Lw)係在1~15mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在－0.25~0.25的範圍。The molding material of the present invention is a molding material composed of 20 to 65% by weight of thermoplastic resin fibers and 35 to 80% by weight of carbon fibers, and is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber. The weight average fiber length (Lw) of the carbon fiber is in the range of 1 to 15 mm, and the orientation parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25.

於本發明的成形材料中，碳纖維的重量含有率，就相對於成形材料而言，係35~80重量%，較佳係38~75重量%，更佳係40~70重量%。碳纖維的重量含有率若低於35重量%，則纖維強化熱可塑性樹脂成形體的力學特性在作為構造零件上會不足。再者，於纖維強化熱可塑性樹脂成形體的成形步驟中，由於成形材料會流動，碳纖維配向於流動方向中，故會損害力學特性的各向同性。又，碳纖維的重量含有率若超過80重量%，則對於碳纖維而言的熱可塑性樹脂之量係根本地變少，會顯著降低纖維強化熱可塑性樹脂成形體的力學特性。In the molding material of the present invention, the weight ratio of the carbon fibers is 35 to 80% by weight, preferably 38 to 75% by weight, and more preferably 40 to 70% by weight based on the molding material. When the weight content of the carbon fiber is less than 35% by weight, the mechanical properties of the fiber-reinforced thermoplastic resin molded article may be insufficient as structural members. Further, in the molding step of the fiber-reinforced thermoplastic resin molded body, since the molding material flows and the carbon fibers are aligned in the flow direction, the isotropy of the mechanical properties is impaired. In addition, when the weight content of the carbon fiber exceeds 80% by weight, the amount of the thermoplastic resin for the carbon fiber is substantially reduced, and the mechanical properties of the fiber-reinforced thermoplastic resin molded article are remarkably lowered.

本發明的成形材料，因為係由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，故單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維構成3次元的網目體。因此，於製造成形材料的步驟或用成形材料來製造纖維強化熱可塑性樹脂成形體的步驟中，可減少碳纖維及熱可塑性樹脂纖維之原料脫落，而且因為提高成形材料的強度，故可得到操作性良好的成形材料。碳纖維與熱可塑性樹脂纖維若為束狀，則由於碳纖維與熱可塑性樹脂纖維的絡合少，故碳纖維及熱可塑性樹脂纖維的原料脫落變多，而且成形材料的強度有降低的情形。再者，熱可塑性樹脂若為粒子狀，則不能在成形材料中保持熱可塑性樹脂，熱可塑性樹脂粒子的原料脫落有變多的情形。Since the molding material of the present invention is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber, the single-fiber carbon fiber and the single-fiber thermoplastic resin fiber constitute a three-dimensional mesh body. Therefore, in the step of producing a molding material or the step of producing a fiber-reinforced thermoplastic resin molded body from a molding material, the raw material of the carbon fiber and the thermoplastic resin fiber can be reduced, and the workability can be improved by increasing the strength of the molding material. Good forming material. When the carbon fiber and the thermoplastic resin fiber are in a bundle shape, since the carbon fiber and the thermoplastic resin fiber are less complexed, the raw material of the carbon fiber and the thermoplastic resin fiber is excessively removed, and the strength of the molding material is lowered. In addition, when the thermoplastic resin is in the form of particles, the thermoplastic resin cannot be held in the molding material, and the raw material of the thermoplastic resin particles may be peeled off.

本發明的成形材料，從構成上述網目體的觀點來看，熱可塑性樹脂纖維較佳為與至少2條以上的碳纖維相接，更佳為與3條以上、尤佳為與5條以上、特佳為與10本以上的碳纖維相接。In the molding material of the present invention, the thermoplastic resin fiber is preferably in contact with at least two or more carbon fibers from the viewpoint of constituting the mesh body, more preferably three or more, and particularly preferably five or more. Jia is connected to more than 10 carbon fibers.

本發明的成形材料之碳纖維的重量平均纖維長度(Lw)係1~15mm，較佳係1.5~12.5mm，更佳係2~10mm。碳纖維的重量平均纖維長度(Lw)若低於1mm，則作為構造零件的力學特性會不足，而若超過15mm，則碳纖維不能成為單纖維狀，在成形體中會發生空隙，力學特性會降低。The carbon fiber of the molding material of the present invention has a weight average fiber length (Lw) of 1 to 15 mm, preferably 1.5 to 12.5 mm, more preferably 2 to 10 mm. When the weight average fiber length (Lw) of the carbon fiber is less than 1 mm, the mechanical properties of the structural component are insufficient, and if it exceeds 15 mm, the carbon fiber cannot be formed into a single fiber, and voids are formed in the molded body, and mechanical properties are lowered.

本發明的成形材料，從力學特性的觀點看，碳纖維的數平均纖維長度(Ln)較佳係1~15mm，更佳係1.5~12.5mm，特佳係2~10mm。In the molding material of the present invention, the number average fiber length (Ln) of the carbon fibers is preferably from 1 to 15 mm, more preferably from 1.5 to 12.5 mm, and particularly preferably from 2 to 10 mm, from the viewpoint of mechanical properties.

此處，成形材料的重量平均纖維長度(Lw)及數平均纖維長度(Ln)，係藉由與纖維強化熱可塑性樹脂成形體的重量平均纖維長度(Lw)及數平均纖維長度(Ln)的測定方法同樣的方法來測定。Here, the weight average fiber length (Lw) and the number average fiber length (Ln) of the molding material are based on the weight average fiber length (Lw) and the number average fiber length (Ln) of the fiber-reinforced thermoplastic resin molded body. The measurement method was measured in the same manner.

於本發明的成形材料表面中，碳纖維的配向狀態係以配向參數(fp)來表示。於本發明中，成形材料的配向參數(fp)若在－0.25~0.25的範圍，則成形材料表面的碳纖維係實質任意配置的狀態，可充分展現本發明的效果，其較佳係在－0.2~0.2的範圍，更佳係在－0.15~0.15的範圍。配向參數(fp)若低於－0.25，或fp若超過0.25，則碳纖維的配向偏差變大，會損害成形體的力學特性之各向同性。In the surface of the molding material of the present invention, the alignment state of the carbon fibers is represented by the alignment parameter (fp). In the present invention, when the alignment parameter (fp) of the molding material is in the range of -0.25 to 0.25, the carbon fibers on the surface of the molding material are substantially arbitrarily disposed, and the effects of the present invention can be sufficiently exhibited, and it is preferably at -0.2. The range of ~0.2 is better in the range of -0.15 to 0.15. When the alignment parameter (fp) is less than -0.25, or if fp exceeds 0.25, the misalignment of the carbon fibers becomes large, and the isotropy of the mechanical properties of the molded body is impaired.

本發明的成形材料之配向參數(fp)，係為將自成形材料表面起的深度100μm的部分中之碳纖維的纖維配向分布以－1.0~1.0的數值所表示的參數，藉由以下方法來測定。切出成形材料的一部分，包埋於環氧樹脂中，研磨到自成形材料表面起100μm的深度為止，以製成觀察用試驗片。除了製作該觀察用試驗片以外，係藉由與纖維強化熱可塑性樹脂成形體的配向參數(fp)同樣的方法來測定。The alignment parameter (fp) of the molding material of the present invention is a parameter represented by a value of -1.0 to 1.0 in the fiber orientation distribution of the carbon fiber in the portion having a depth of 100 μm from the surface of the molding material, and is determined by the following method. . A part of the molding material was cut out, embedded in an epoxy resin, and ground to a depth of 100 μm from the surface of the molding material to prepare a test piece for observation. The test piece for observation was produced by the same method as the alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article.

本發明的成形材料，從使成形體的力學特性成為各向同性的觀點來看，於碳纖維的配向角度度數分布中，30°刻紋的相對度數之最大值較佳係0.29以下，更佳係0.26以下，特佳係0.23以下。而且本發明的成形材料，從使成形體的力學特性成為各向同性的觀點來看，於碳纖維的配向角度度數分布中，30°刻紋的相對度數之最小值較佳係0.03以上，更佳係0.06以上，特佳係0.10以上。成形材料表面的碳纖維之配向角度度數分布中的30°刻紋之相對度數，係表示成形材料表面的碳纖維之配向角度分布的指標，於本發明中將自成形材料表面起的深度100μm的部分之碳纖維的配向角度，表示成30°刻紋的相對度數。作為成形材料表面的碳纖維之配向角度度數分布中之30°刻紋的相對度數之測定方法，係藉由與纖維強化熱可塑性樹脂成形體同樣的方法來測定。In the molding material of the present invention, from the viewpoint of the isotropy of the mechanical properties of the molded body, the maximum value of the relative degree of the 30° engraving in the distribution angle degree distribution of the carbon fibers is preferably 0.29 or less. 0.26 or less, particularly preferably 0.23 or less. Further, in the molding material of the present invention, from the viewpoint of making the mechanical properties of the molded body isotropy, in the distribution angle degree distribution of the carbon fibers, the minimum value of the relative degree of the 30° embossing is preferably 0.03 or more, more preferably It is 0.06 or more, and is particularly preferably 0.10 or more. The relative degree of the 30° engraving in the distribution angle degree distribution of the carbon fibers on the surface of the molding material is an index indicating the distribution angle of the carbon fibers on the surface of the molding material, and a portion having a depth of 100 μm from the surface of the molding material in the present invention The angle of alignment of the carbon fibers is expressed as the relative degree of the 30° engraving. The method of measuring the relative degree of the 30° scribe in the distribution angle degree distribution of the carbon fibers on the surface of the molding material was measured by the same method as the fiber-reinforced thermoplastic resin molded body.

本發明的成形材料，從操作性的觀點來看，所含有的碳纖維之分散參數較佳係0~25%，更佳係0~22%，特佳係0~20%。所謂成形材料的分散參數，係表示成形材料中所含有的碳纖維的重量含有率之變動度的指標，以於本發明的成形材料剖面中所測定的碳纖維條數之變動度的值來表示。成形材料的分散參數之測定，係藉由切出一部分的成形材料，包埋於環氧樹脂中，研磨成形材料剖面以製作觀察用試驗片，以外係藉由與前述纖維強化熱可塑性樹脂成形體的分散參數同樣的方法來測定。The molding material of the present invention preferably has a dispersion parameter of 0 to 25%, more preferably 0 to 22%, and particularly preferably 0 to 20%, from the viewpoint of workability. The dispersion parameter of the molding material is an index indicating the degree of change in the weight content of the carbon fibers contained in the molding material, and is expressed by the value of the degree of change in the number of carbon fibers measured in the cross section of the molding material of the present invention. The measurement of the dispersion parameter of the molding material is carried out by cutting a part of the molding material, embedding it in the epoxy resin, and polishing the cross section of the molding material to prepare a test piece for observation, and the thermoplastic resin molded body by the fiber reinforcement described above. The same parameters are used to determine the dispersion parameters.

本發明的成形材料，從構成上述網目體的觀點來看，碳纖維的重量平均纖維長度(Lw)與數平均纖維長度(Ln)之比(Lw/Ln)，較佳係在1.0~2.5的範圍，更佳係在1.0~2.2的範圍，特佳係在1.0~2.0的範圍。此處，重量平均纖維長度(Lw)與數平均纖維長度(Ln)的比(Lw/Ln)為1.0時，係表示僅由相同長度的纖維所構成，意味隨著重量平均纖維長度(Lw)與數平均纖維長度(Ln)之比(Lw/Ln)之變大，纖維長度的分布變廣。In the molding material of the present invention, the ratio of the weight average fiber length (Lw) of the carbon fibers to the number average fiber length (Ln) (Lw/Ln) is preferably in the range of 1.0 to 2.5 from the viewpoint of constituting the mesh body. More preferably, it is in the range of 1.0 to 2.2, and the best is in the range of 1.0 to 2.0. Here, when the ratio (Lw/Ln) of the weight average fiber length (Lw) to the number average fiber length (Ln) is 1.0, it means that it is composed only of fibers of the same length, meaning that the fiber length (Lw) is equal to the weight. The ratio of the number average fiber length (Ln) (Lw/Ln) becomes larger, and the distribution of the fiber length becomes wider.

本發明的成形材料，從操作性的觀點來看，較佳為片狀。所謂片狀的成形材料，就是相對於長度方向或寬度方向而言，厚度小、薄的寬廣成形材料，例如棉網、不織布、氈、蓆等。The molding material of the present invention is preferably in the form of a sheet from the viewpoint of workability. The sheet-shaped molding material is a wide and thin molding material having a small thickness and a small thickness in the longitudinal direction or the width direction, such as a cotton net, a non-woven fabric, a felt, a mat, and the like.

「碳纖維」"carbon fiber"

本發明的成形材料所用的碳纖維，較佳可使用與上述纖維強化熱可塑性樹脂成形體所用的碳纖維同樣的碳纖維。The carbon fiber used for the molding material of the present invention is preferably a carbon fiber similar to the carbon fiber used for the fiber-reinforced thermoplastic resin molded article.

本發明的成形材料所用的碳纖維，較佳可使用具有與上述纖維強化熱可塑性樹脂成形體所用的碳纖維同樣之拉伸強度和拉伸彈性模數的碳纖維。The carbon fiber used for the molding material of the present invention is preferably a carbon fiber having the same tensile strength and tensile modulus as that of the carbon fiber used for the fiber-reinforced thermoplastic resin molded article.

「熱可塑性樹脂」"thermoplastic resin"

本發明的成形材料所用的熱可塑性樹脂，較佳可使用與上述纖維強化熱可塑性樹脂成形體所用的熱可塑性樹脂同樣之熱可塑性樹脂。The thermoplastic resin used for the molding material of the present invention is preferably a thermoplastic resin similar to the thermoplastic resin used for the above-mentioned fiber-reinforced thermoplastic resin molded article.

「添加劑、填充劑等」"Additives, fillers, etc."

於本發明的成形材料中，亦可含有在上述纖維強化熱可塑性樹脂成形體中所進一步添加的添加劑、填充劑等同樣的添加劑、填充劑等。The molding material of the present invention may contain the same additives and fillers as those added to the fiber-reinforced thermoplastic resin molded article, a filler, and the like.

「用途」"use"

作為本發明的成形材料之用途，較佳可適用於與上述纖維強化熱可塑性樹脂成形體同樣的用途。The use of the molding material of the present invention is preferably applied to the same application as the above-mentioned fiber-reinforced thermoplastic resin molded article.

『成形材料的製造方法』"Manufacturing method of forming materials"

以下說明成形材料的製造方法。The method of producing the molding material will be described below.

作為成形材料的製造方法，只要是能得到上述成形材料的方法即可，而沒有特別的限制。例如可舉出：(1)在氣流噴射下將具有短切形態的碳纖維束和熱可塑性樹脂纖維作開鬆、混合，使其混合物聚集於輸送帶上的氣流噴射法，(2)於分散液中將具有短切形態的碳纖維和熱可塑性樹脂纖維作開鬆、混合，在有孔支持體上造紙的造紙法，及(3)藉由切割機對具有短切形態的碳纖維和熱可塑性樹脂纖維作開鬆、混合，使其混合物聚集於輸送帶上的乾式法等。於本發明中，更佳為使用碳纖維和熱可塑性樹脂纖維的開鬆性優良且可長地維持該碳纖維的纖維長度之氣流噴射法或造紙法，從生產性的觀點來看，更佳為使用造紙法。The method for producing the molding material is not particularly limited as long as it can obtain the above-mentioned molding material. For example, (1) an air jet method in which a carbon fiber bundle having a chopped shape and a thermoplastic resin fiber are opened and mixed under a jet of air to aggregate the mixture on a conveyor belt, and (2) a dispersion liquid a carbon paper having a chopped form and a thermoplastic resin fiber for opening and mixing, a papermaking method for making paper on a porous support, and (3) a carbon fiber and a thermoplastic resin fiber having a chopped shape by a cutter A dry method of opening, mixing, and aggregating the mixture on a conveyor belt. In the present invention, it is more preferable to use a gas jet method or a papermaking method in which the carbon fiber and the thermoplastic resin fiber are excellent in opening property and can maintain the fiber length of the carbon fiber, and it is more preferable from the viewpoint of productivity. Papermaking method.

又，於氣流噴射法中，藉由控制氣流的流動，亦可以單纖維狀均勻混合碳纖維和熱可塑性樹脂纖維，可提高成形材料的各向同性。於造紙法中，藉由降低對於分散液量而言的碳纖維之濃度，或使攪拌分散液的攪拌翼成為攪拌力大的形狀，或提高攪拌翼的轉數，可以單纖維狀均勻混合碳纖維和熱可塑性樹脂纖維，可提高成形材料的各向同性、碳纖維。Further, in the air jet method, by controlling the flow of the air current, the carbon fibers and the thermoplastic resin fibers can be uniformly mixed in a single fiber shape, and the isotropy of the molding material can be improved. In the papermaking method, by reducing the concentration of the carbon fiber for the amount of the dispersion, or by making the stirring blade of the stirring dispersion into a shape having a large stirring force, or increasing the number of rotations of the stirring blade, the carbon fiber can be uniformly mixed in a single fiber form. The thermoplastic resin fiber can improve the isotropy of the molding material and the carbon fiber.

『纖維強化熱可塑性樹脂成形體的製造方法』"Method for producing fiber-reinforced thermoplastic resin molded body"

接著，說明本發明的纖維強化熱可塑性樹脂成形體之製造方法。Next, a method of producing the fiber-reinforced thermoplastic resin molded article of the present invention will be described.

於本發明的製造方法中，藉由含有至少以下(I)~(V)的步驟之壓縮成形法來使上述成形材料成形。In the production method of the present invention, the molding material is formed by a compression molding method including at least the following steps (I) to (V).

(I)將成形材料所含有熱可塑性樹脂加熱熔融之步驟，(Ⅱ)將成形材料配置於模具中之步驟，(Ⅲ)以模具來加壓成形材料之步驟，(Ⅳ)在模具內將成形材料固化之步驟，(V)打開模具，將纖維強化熱可塑性樹脂成形體脫模之步驟。(I) a step of heating and melting the thermoplastic resin contained in the molding material, (II) a step of disposing the molding material in the mold, (III) a step of pressing the molding material with a mold, and (IV) forming the mold in the mold. The step of curing the material, (V) the step of opening the mold to demold the fiber-reinforced thermoplastic resin molded body.

藉由將上述成形材料壓縮成形，可長地維持強化纖維的纖維長度，可實質地任意配置碳纖維，可成為力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體。例如，於射出成形中，藉由使碳纖維的纖維長度變短，使碳纖維配向於流動方向，則纖維強化熱可塑性樹脂成形體的力學特性會降低，而且會損害其各向同性。作為壓縮成形法，係沒有特別的限制，例如可舉出衝壓成形或高壓加壓成形等。By compressing and molding the above-mentioned molding material, the fiber length of the reinforcing fiber can be maintained long, and the carbon fiber can be substantially arbitrarily disposed, and the fiber-reinforced thermoplastic resin molded article having excellent mechanical properties and isotropy can be obtained. For example, in the injection molding, when the fiber length of the carbon fiber is shortened and the carbon fiber is aligned in the flow direction, the mechanical properties of the fiber-reinforced thermoplastic resin molded article are lowered, and the isotropy is impaired. The compression molding method is not particularly limited, and examples thereof include press molding and high pressure press molding.

於上述(I)步驟中，就加熱溫度而言，從成形材料的賦形性及熱可塑性樹脂的劣化之觀點來看，當成形材料的熱可塑性樹脂為結晶性樹脂時，較佳係使成形材料的溫度在熱可塑性樹脂的熔點以上且在(熔點＋80)℃以下的範圍，當成形材料的熱可塑性樹脂為非結晶性樹脂時，較佳係使成形材料的溫度在熱可塑性樹脂的(玻璃轉移溫度＋60)℃以上且在(玻璃轉移溫度＋200)℃以下的範圍。In the above step (I), in terms of the heating temperature, from the viewpoint of the formability of the molding material and the deterioration of the thermoplastic resin, when the thermoplastic resin of the molding material is a crystalline resin, it is preferred to form the molding. The temperature of the material is above the melting point of the thermoplastic resin and in the range of (melting point + 80) ° C or less. When the thermoplastic resin of the molding material is an amorphous resin, it is preferred to make the temperature of the molding material in the thermoplastic resin (glass) The transfer temperature is +60) ° C or more and is in the range of (glass transition temperature + 200) ° C or less.

於上述(I)步驟中，作為加熱熔融成形材料所含有的熱可塑性樹脂之方法，並沒有特別的限制，例如可使用熱風加熱、遠紅外線加熱、近紅外線加熱、熱板接觸、熱輥接觸、振動加熱等向來習知的方法。In the above step (I), the method of heating the thermoplastic resin contained in the melt-molding material is not particularly limited, and for example, hot air heating, far-infrared heating, near-infrared heating, hot plate contact, hot roll contact, or the like may be used. A conventional method such as vibration heating.

於上述(I)步驟中，從熱可塑性樹脂的劣化之觀點來看，更佳為在氮氣或氬氣等的惰性氣體氣氛下或在減壓下進行加熱熔融。In the above step (I), from the viewpoint of deterioration of the thermoplastic resin, it is more preferable to carry out heating and melting under an inert gas atmosphere such as nitrogen or argon or under reduced pressure.

從熱可塑性樹脂的劣化之觀點來看，亦可以於上述(I)步驟之前，增加去除成形材料中所含有的水分之步驟。作為去除成形材料中所含有的水分之方法，係沒有特別的限制，例如可以使用熱風乾燥、遠紅外線乾燥、近紅外線乾燥、真空乾燥、減壓吸氣、遠心分離等向來習知的方法。From the viewpoint of deterioration of the thermoplastic resin, the step of removing moisture contained in the molding material may be added before the step (I). The method of removing the moisture contained in the molding material is not particularly limited, and for example, a conventional method such as hot air drying, far infrared ray drying, near infrared ray drying, vacuum drying, vacuum suction, and telecentric separation can be used.

於上述(Ⅱ)、(Ⅲ)步驟中，從成形材料的賦形性之觀點來看，較佳為在熱可塑性樹脂成熔融狀態下將成形材料配置於模具中，在熱可塑性樹脂為熔融狀態下將成形材料加壓。In the above steps (II) and (III), from the viewpoint of the formability of the molding material, it is preferred that the molding material is placed in a mold in a molten state in a molten state, and the thermoplastic resin is in a molten state. The forming material is pressed under.

於上述(Ⅱ)步驟中，當使具有厚度不同部位的纖維強化熱可塑性樹脂成形體成形時，從成形材料的賦形性的觀點來看，亦可將成形材料以數個積層，配置在模具中。In the step (II), when the fiber-reinforced thermoplastic resin molded body having a portion having a different thickness is formed, the molding material may be placed in the mold in a plurality of layers from the viewpoint of the formability of the molding material. in.

於上述(Ⅱ)步驟中，從纖維強化熱可塑性樹脂成形體的力學特性之各向同性的觀點來看，裝料率較佳為80%以上，更佳為90%以上，特佳為95%以上。裝料率係指對於模具的模腔面積而言，成形材料的面積之比率。In the step (II), the charging ratio is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more from the viewpoint of isotropy of the mechanical properties of the fiber-reinforced thermoplastic resin molded article. . The charging rate refers to the ratio of the area of the forming material to the cavity area of the mold.

於上述(Ⅱ)~(V)步驟中，就模具溫度而言，從纖維強化熱可塑性樹脂成形體的脫模性之觀點來看，當熱可塑性樹脂為結晶性樹脂時，較佳係使成形材料的溫度成為熱可塑性樹脂的(熔點－30)℃以下，當熱可塑性樹脂為非結晶性樹脂時，較佳係使成形材料的溫度成為熱可塑性樹脂的(玻璃轉移溫度＋50)℃以下。此處的模具溫度係指模具的模腔表面溫度。In the above steps (II) to (V), in terms of the mold temperature, from the viewpoint of mold release property of the fiber-reinforced thermoplastic resin molded body, when the thermoplastic resin is a crystalline resin, it is preferred to form the mold. The temperature of the material becomes a thermoplastic resin (melting point: -30) ° C or less. When the thermoplastic resin is an amorphous resin, it is preferred that the temperature of the molding material be a thermoplastic resin (glass transition temperature + 50) ° C or less. The mold temperature here refers to the cavity surface temperature of the mold.

於上述(Ⅲ)步驟中，較佳為進行至少1次以上的去除對成形材料的加壓，再度將成形材料加壓的操作。藉由去除對成形材料的加壓，再度將成形材料加壓，則可將模腔內的空氣或成形材料內所含有的空氣壓出模具外。該操作係使纖維強化熱可塑性樹脂成形體的空隙率成為5%以下為止，較佳係成為3%以下為止，更佳係成為2%以下為止，可重複進行。In the above step (III), it is preferred to carry out the operation of pressurizing the molding material by at least one or more removal of the molding material. By removing the pressurization of the molding material and pressurizing the molding material again, the air contained in the cavity or the air contained in the molding material can be pushed out of the mold. In this operation, the porosity of the fiber-reinforced thermoplastic resin molded article is 5% or less, preferably 3% or less, more preferably 2% or less, and it can be repeated.

以下，藉由實施例來具體的說明本發明的成形材料及纖維強化熱可塑性樹脂成形體，惟下述實施例不限制本發明。Hereinafter, the molding material and the fiber-reinforced thermoplastic resin molded article of the present invention will be specifically described by way of examples, but the following examples are not intended to limit the invention.

以下，說明本實施例及比較例所用的各評價方法。Hereinafter, each evaluation method used in the present embodiment and the comparative example will be described.

(1)纖維長度、重量平均纖維長度(Lw)及數平均纖維長度(Ln)的測定方法(1) Method for measuring fiber length, weight average fiber length (Lw), and number average fiber length (Ln)

切出成形材料或纖維強化熱可塑性樹脂成形體的一部分，藉由能溶解母體樹脂(熱可塑性樹脂)的溶劑來充分溶解母體樹脂後，藉由過濾等的習知操作使與碳纖維分離。於沒有溶解母體樹脂的溶劑時，切出成形材料或纖維強化熱可塑性樹脂成形體的一部分，在500℃的溫度加熱2小時，燒掉熱可塑性樹脂纖維以分離出碳纖維。從所分離的碳纖維任意地抽出400條，以光學顯微鏡或掃描型電子顯微鏡來測定其長度直到1μm單位為止，依照下式求出其重量平均纖維長度(Lw)及數平均纖維長度(Ln)。A part of the molding material or the fiber-reinforced thermoplastic resin molded body is cut out, and the matrix resin is sufficiently dissolved by a solvent capable of dissolving the matrix resin (thermoplastic resin), and then separated from the carbon fibers by a conventional operation such as filtration. When the solvent of the matrix resin was not dissolved, a part of the molding material or the fiber-reinforced thermoplastic resin molded body was cut out, and heated at a temperature of 500 ° C for 2 hours to burn off the thermoplastic resin fibers to separate the carbon fibers. 400 pieces of carbon fibers were arbitrarily extracted from the separated carbon fibers, and the length was measured up to 1 μm unit by an optical microscope or a scanning electron microscope, and the weight average fiber length (Lw) and the number average fiber length (Ln) were determined according to the following formula.

．重量平均纖維長度(Lw)＝Σ(Li×Wi/100)．數平均纖維長度(Ln)＝(ΣLi)/400．Li：所測定的纖維長度(i＝1、2、3、．．．、400)．Wi：纖維長度Li的纖維之重量分率(i＝1、2、3、．．．、400). Weight average fiber length (Lw) = Σ (Li × Wi / 100). Number average fiber length (Ln) = (ΣLi) / 400. Li: measured fiber length (i = 1, 2, 3, ..., 400). Wi: weight fraction of fibers of fiber length Li (i = 1, 2, 3, ..., 400)

再者，若任意抽出的測定碳纖維條數為400本以上的話，則所算出的碳纖維之重量平均纖維長度(Lw)及數平均纖維長度(Ln)的值係幾乎成為沒有變化。In addition, when the number of the measured carbon fibers arbitrarily extracted is 400 or more, the calculated values of the weight average fiber length (Lw) and the number average fiber length (Ln) of the carbon fibers are almost unchanged.

(2)分散參數評價方法(2) Dispersion parameter evaluation method

切出一部分的纖維強化熱可塑性樹脂成形體，將所切出的試驗片包埋於環氧樹脂中，研磨纖維強化熱可塑性樹脂成形體的剖面，以製作觀察用試驗片。A part of the fiber-reinforced thermoplastic resin molded body was cut out, and the cut test piece was embedded in an epoxy resin, and the cross section of the fiber-reinforced thermoplastic resin molded body was polished to prepare a test piece for observation.

又，切出一部分的成形材料，以具有與所切出的試驗片同樣大小的2片玻璃板來夾住成形材料，以夾具抓住、固定。在該狀態下，包埋於環氧樹脂中，研磨成形材料的剖面，以製作觀察用試驗片。Further, a part of the molding material was cut out, and the molding material was sandwiched between two glass sheets having the same size as the cut test piece, and grasped and fixed by a jig. In this state, it was embedded in an epoxy resin, and the cross section of the molding material was polished to prepare a test piece for observation.

用光學顯微鏡來觀察經研磨所得到的纖維強化熱可塑性樹脂成形體或成形材料的剖面，任意地選出10處的0.1mm×0.1mm之範圍，測定該範圍內所含有的碳纖維之條數。以所選出的10處之碳纖維的條數平均值當作A，以標準偏差當作S，藉由下式來求得分散參數。The cross section of the fiber-reinforced thermoplastic resin molded article or the molded material obtained by the polishing was observed with an optical microscope, and the range of 0.1 mm × 0.1 mm at 10 places was arbitrarily selected, and the number of carbon fibers contained in the range was measured. The average value of the number of carbon fibers at the selected 10 places was taken as A, and the standard deviation was taken as S, and the dispersion parameter was obtained by the following formula.

．分散參數＝(100×S/A)(單位：%). Dispersion parameter = (100 × S / A) (unit: %)

又，纖維強化熱可塑性樹脂成形體或成形材料的分散參數之測定用試驗片，係廻避纖維強化熱可塑性樹脂成形體或成形材料的端部，儘可能地使用中央附近之沒有突面、肋條和成形體的厚度變化之部分。In the test piece for measuring the dispersion parameter of the fiber-reinforced thermoplastic resin molded article or the molding material, the end portion of the fiber-reinforced thermoplastic resin molded body or the molding material is avoided, and as far as possible, no protruding surface, ribs, and The portion of the thickness of the shaped body that changes.

作為表示纖維強化熱可塑性樹脂成形體或成形材料中所含有的碳纖維之重量含有率的變動度之指標，測定纖維強化熱可塑性樹脂成形體或成形材料之剖面的分散參數，藉由以下4個等級來評價。○○和○係合格，△和×係不合格。The index of the variation in the weight content of the carbon fiber contained in the fiber-reinforced thermoplastic resin molded article or the molded material is measured, and the dispersion parameters of the cross section of the fiber-reinforced thermoplastic resin molded article or the molded material are measured, and the following four grades are used. To evaluate. ○○ and ○ were qualified, and △ and × were unqualified.

○○：分散參數低於20%。○○: The dispersion parameter was less than 20%.

○：分散參數係20%以上且低於25%。○: The dispersion parameter is 20% or more and less than 25%.

△：分散參數係25%以上且低於30%。△: The dispersion parameter is 25% or more and less than 30%.

×：分散參數係30%以上。×: The dispersion parameter is 30% or more.

(3)配向參數(fp)評價方法(3) Directional parameter (fp) evaluation method

切出纖維強化熱可塑性樹脂成形體的一部分，將所切出的試驗片包埋在環氧樹脂中，將纖維強化熱可塑性樹脂成形體表面研磨到自纖維強化熱可塑性樹脂成形體的表面起100μm的深度為止，以製成觀察用試驗片。A part of the fiber-reinforced thermoplastic resin molded body is cut out, and the cut test piece is embedded in an epoxy resin, and the surface of the fiber-reinforced thermoplastic resin molded body is ground to 100 μm from the surface of the fiber-reinforced thermoplastic resin molded body. The depth of the test was made to prepare a test piece for observation.

又，切出一部分的成形材料，將所切出的試驗片包埋在環氧樹脂中，將成形材料表面研磨到自成形材料的表面起100μm的深度為止，以製成觀察用試驗片。Further, a part of the molding material was cut out, and the cut test piece was embedded in an epoxy resin, and the surface of the molding material was polished to a depth of 100 μm from the surface of the molding material to prepare a test piece for observation.

用光學顯微鏡來觀察纖維強化熱可塑性樹脂成形體或成形材料的觀察用試驗片，任意地選出400條碳纖維。碳纖維的研磨面一般係成為橢圓形，以該橢圓的長軸方向當作纖維的配向方向。接著，任意設定1條成為角度基準的基準直線，測定全部相對於基準直線而言所選出的碳纖維之配向方向所成的角度(以下簡稱配向角度αi)。配向角度αi係測定相對於基準直線而言，反時針旋轉方向的角度，其為0°以上且小於180°的角度。使用該配向角度αi，藉由下式求得纖維強化熱可塑性樹脂成形體或成形材料的配向參數(fp)。The test piece for observation of the fiber-reinforced thermoplastic resin molded article or the molded material was observed with an optical microscope, and 400 carbon fibers were arbitrarily selected. The polished surface of the carbon fiber is generally elliptical, and the long axis direction of the ellipse is taken as the alignment direction of the fiber. Then, one reference line which is an angle reference is arbitrarily set, and an angle (hereinafter referred to as an alignment angle αi) of all the directions of the carbon fibers selected with respect to the reference line is measured. The alignment angle αi is an angle measured in the counterclockwise direction with respect to the reference straight line, and is an angle of 0° or more and less than 180°. Using the alignment angle αi, the alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article or the molding material was determined by the following formula.

fp＝2×Σ(cos2αi/400)－1．αi：所測定的配向角度(i＝1、2、3、．．．、400)Fp=2×Σ(cos2αi/400)-1. Ii: measured angle of alignment (i = 1, 2, 3, ..., 400)

又，作為纖維強化熱可塑性樹脂成形體或成形材料的「配向參數」之測定用試驗片，係廻避纖維強化熱可塑性樹脂成形體或成形材料的端部，儘可能地使用中央附近之沒有突面、肋條和成形體之厚度變化的部分來進行測定。In the test piece for measuring the "alignment parameter" of the fiber-reinforced thermoplastic resin molded article or the molded material, the end portion of the fiber-reinforced thermoplastic resin molded body or the molded material is avoided, and the unprotrusion near the center is used as much as possible. The ribs and the portions of the molded body whose thickness is changed are measured.

作為碳纖維之任意配置的指標，測定纖維強化熱可塑性樹脂成形體或成形材料的配向參數(fp)，藉由以下4個等級來評價。○○和○係合格，△和×係不合格。The alignment parameter (fp) of the fiber-reinforced thermoplastic resin molded article or the molded material was measured as an index of the arbitrary arrangement of the carbon fibers, and was evaluated by the following four grades. ○○ and ○ were qualified, and △ and × were unqualified.

○○：fp係「－0.15≦fp≦0.15」。○○: fp is "-0.15≦fp≦0.15".

○：fp係「－0.25≦fp<－0.15」或「0.15<fp≦0.25」。○: fp is "-0.25≦fp<-0.15" or "0.15<fp≦0.25".

△：fp係「－0.35≦fp<－0.25」或「0.25<fp≦0.35」。△: fp is "-0.35≦fp<-0.25" or "0.25<fp≦0.35".

×：fp係「－1≦fp<－0.35」或「0.35<fp≦1」。×: fp is "-1≦fp<-0.35" or "0.35<fp≦1".

(4)配向角度分布的評價方法(4) Evaluation method of alignment angle distribution

切出纖維強化熱可塑性樹脂成形體的一部分，將所切出的試驗片包埋在環氧樹脂中，將纖維強化熱可塑性樹脂成形體表面研磨到自纖維強化熱可塑性樹脂成形體之表面起100μm的深度為止，以製成觀察用試驗片。A part of the fiber-reinforced thermoplastic resin molded body was cut out, and the cut test piece was embedded in an epoxy resin, and the surface of the fiber-reinforced thermoplastic resin molded body was polished to 100 μm from the surface of the fiber-reinforced thermoplastic resin molded body. The depth of the test was made to prepare a test piece for observation.

又，切出一部分的成形材料，將所切出的試驗片包埋在環氧樹脂中，將成形材料表面研磨到自成形材料的表面起100μm的深度為止，以製成觀察用試驗片。Further, a part of the molding material was cut out, and the cut test piece was embedded in an epoxy resin, and the surface of the molding material was polished to a depth of 100 μm from the surface of the molding material to prepare a test piece for observation.

用光學顯微鏡來觀察纖維強化熱可塑性樹脂成形體或成形材料的觀察用試驗片，任意地選出400條碳纖維。碳纖維的研磨面一般係成為橢圓形，以該橢圓的長軸方向當作纖維的配向方向。接著，任意設定1條成為角度基準的基準直線，測定全部相對於基準直線而言所選出的碳纖維之配向方向所成的角度(以下簡稱配向角度αi)。配向角度αi係測定相對於基準直線而言，反時針旋轉方向的角度，其為0°以上且小於180°的角度。此配向角度αi的30°刻紋的相對度數係藉由下式求得。The test piece for observation of the fiber-reinforced thermoplastic resin molded article or the molded material was observed with an optical microscope, and 400 carbon fibers were arbitrarily selected. The polished surface of the carbon fiber is generally elliptical, and the long axis direction of the ellipse is taken as the alignment direction of the fiber. Then, one reference line which is an angle reference is arbitrarily set, and an angle (hereinafter referred to as an alignment angle αi) of all the directions of the carbon fibers selected with respect to the reference line is measured. The alignment angle αi is an angle measured in the counterclockwise direction with respect to the reference straight line, and is an angle of 0° or more and less than 180°. The relative degree of the 30° engraving of the alignment angle αi is obtained by the following equation.

．αi：所測定的配向角度(i＝1、2、．．、400)．N0~30：0≦配向角度αi<30的碳纖維之條數(i＝1、2、．．、400)．N30~60：30≦配向角度αi<60的碳纖維之條數(i＝1、2、．．、400)．N60~90：60≦配向角度αi<90的碳纖維之條數(i＝1、2、．．、400)．N90~120：90≦配向角度αi<120的碳纖維之條數(i＝1、2、．．、400)．N120~150：120≦配向角度αi<150的碳纖維之條數(i＝1、2、．．、400)．N150~180：150≦配向角度αi<180的碳纖維之條數(i＝1、2、．．、400)．相對度數的最大值＝MAX(N0~30、N30~60、N60~90、N90~120、N120~150、N150~180)/400．相對度數的最小值：MIN(N0~30、N30~60、N60~90、N90~120、N120~150、N150~180)/400. Ii: the measured alignment angle (i=1, 2, .., 400). N0~30:0≦ The number of carbon fibers with the matching angle αi<30 (i=1, 2, .., 400). N30~60: 30≦ The number of carbon fibers with the matching angle αi<60 (i=1, 2, .., 400). N60~90: 60≦ The number of carbon fibers with the matching angle αi<90 (i=1, 2, .., 400). N90~120: 90≦ The number of carbon fibers with the matching angle αi<120 (i=1, 2, .., 400). N120~150: 120≦ The number of carbon fibers with the matching angle αi<150 (i=1, 2, .., 400). N150~180: 150≦ The number of carbon fibers with the matching angle αi<180 (i=1, 2, .., 400). The maximum value of the relative degree = MAX (N0 ~ 30, N30 ~ 60, N60 ~ 90, N90 ~ 120, N120 ~ 150, N150 ~ 180) / 400. Minimum value of relative degree: MIN (N0~30, N30~60, N60~90, N90~120, N120~150, N150~180)/400

又，作為纖維強化熱可塑性樹脂成形體或成形材料的配向角度分布之測定用試驗片，係廻避纖維強化熱可塑性樹脂成形體或成形材料的端部，儘可能地使用中央附近之沒有突面、肋條和成形體的厚度變化之部分。In addition, the test piece for measuring the angular distribution of the orientation of the fiber-reinforced thermoplastic resin molded article or the molded material is formed by avoiding the end portion of the fiber-reinforced thermoplastic resin molded body or the molded material, and using no protruding surface near the center as much as possible. The portion of the rib and the thickness of the formed body that varies.

作為纖維的任意配向性之指標，測定纖維強化熱可塑性樹脂成形體或成形材料的配向角度分布之相對度數的最大值，藉由以下4個等級來評價。○○和○係合格，△和×係不合格。The maximum value of the relative degree of the distribution angle distribution of the fiber-reinforced thermoplastic resin molded article or the molded material was measured as an index of the arbitrary orientation of the fiber, and was evaluated by the following four grades. ○○ and ○ were qualified, and △ and × were unqualified.

○○：相對度數的最大值係0.17以上且0.23以下。○○: The maximum value of the relative power is 0.17 or more and 0.23 or less.

○：相對度數的最大值係比0.23大且為0.29以下。○: The maximum value of the relative power is larger than 0.23 and is 0.29 or less.

△：相對度數的最大值係比0.29大且為0.35以下。Δ: The maximum value of the relative power is larger than 0.29 and is 0.35 or less.

×：相對度數的最大值係比0.35大。×: The maximum value of the relative power is larger than 0.35.

又，作為纖維的任意配向性之指標，測定纖維強化熱可塑性樹脂成形體或成形材料的配向角度分布之相對度數的最小值，藉由以下4個等級來評價。○○和○係合格，△和×係不合格。In addition, the minimum value of the relative degree of the distribution angle distribution of the fiber-reinforced thermoplastic resin molded article or the molded material was measured as an index of the arbitrary orientation of the fiber, and was evaluated by the following four grades. ○○ and ○ were qualified, and △ and × were unqualified.

○○：相對度數的最小值係0.10以上且0.17以下。○○: The minimum value of the relative power is 0.10 or more and 0.17 or less.

○：相對度數的最小值係0.03以上且小於0.10。○: The minimum value of the relative power is 0.03 or more and less than 0.10.

△：相對度數的最小值係0.01以上且小於0.03。△: The minimum value of the relative power is 0.01 or more and less than 0.03.

×：相對度數的最小值係0以上且小於0.01。×: The minimum value of the relative power is 0 or more and less than 0.01.

(5)碳纖維的重量含有率之測定方法(5) Method for measuring the weight content of carbon fibers

從纖維強化熱可塑性樹脂成形體或成形材料切出1cm×1cm的試驗片，投入石英玻璃容器內。將該容器在60℃的溫度進行24小時的真空乾燥，在乾燥器內冷卻到室溫為止後，秤量試驗片與石英玻璃容器的合計重量W1(克)、及石英玻璃容器的重量W0(克)。於容器內裝有試驗片的狀態下，在空氣中於500℃的溫度加熱2小時，燒掉熱可塑性樹脂後，在氮氣氛中冷卻到室溫為止，秤量碳纖維與石英玻璃容器的合計重量W2(克)。經過以上的處理，藉由下式求得纖維強化熱可塑性樹脂成形體或成形材料之碳纖維的重量含有率(Wf)。A test piece of 1 cm × 1 cm was cut out from the fiber-reinforced thermoplastic resin molded body or the molded material, and placed in a quartz glass container. The container was vacuum dried at a temperature of 60 ° C for 24 hours, and after cooling to room temperature in a desiccator, the total weight of the test piece and the quartz glass container W1 (g), and the weight of the quartz glass container W0 (g) were weighed. ). In a state where a test piece is placed in a container, it is heated in air at a temperature of 500 ° C for 2 hours, and the thermoplastic resin is burned off, and then cooled to room temperature in a nitrogen atmosphere, and the total weight of the carbon fiber and the quartz glass container is weighed. (g). Through the above treatment, the weight content (Wf) of the carbon fibers of the fiber-reinforced thermoplastic resin molded article or the molded material was determined by the following formula.

Wf＝100×(W2－W0)/(W1－W0)(單位：重量%)Wf=100×(W2-W0)/(W1-W0) (unit: weight%)

測定數係n＝5，以平均值當作碳纖維的重量含有率(Wf)。The number of measurements is n=5, and the average value is taken as the weight content (Wf) of the carbon fiber.

(6)纖維強化熱可塑性樹脂成形體的密度測定方法(6) Method for measuring density of fiber-reinforced thermoplastic resin molded body

纖維強化熱可塑性樹脂成形體的密度(ρc)，係依照JIS K 7112(1999)之5中所記載的A法(水中置換法)來測定。從纖維強化熱可塑性樹脂成形體切出1cm×1cm的試驗片，在60℃的溫度進行24小時的真空乾燥，以在乾燥器內冷卻到室溫為止者當作試驗片。浸積液係使用乙醇。The density (ρc) of the fiber-reinforced thermoplastic resin molded article is measured in accordance with the A method (aqueous substitution method) described in JIS K 7112 (1999). A test piece of 1 cm × 1 cm was cut out from the fiber-reinforced thermoplastic resin molded body, and vacuum-dried at a temperature of 60 ° C for 24 hours, and was cooled to room temperature in a desiccator as a test piece. Ethanol is used as the impregnation liquid.

(7)纖維強化熱可塑性樹脂成形體的碳纖維之體積含有率及空隙率的評價方法(7) Method for evaluating volume fraction and void ratio of carbon fibers of a fiber-reinforced thermoplastic resin molded article

使用(5)所測定的纖維強化熱可塑性樹脂成形體之碳纖維的重量含有率(Wf)與(6)所測定的纖維強化熱可塑性樹脂成形體的密度(ρc)，藉由下式來求得纖維強化熱可塑性樹脂成形體之碳纖維的體積含有率(Vf)、熱可塑性樹脂的體積含有率(Vr)、及空隙率(Vv)。The weight content (Wf) of the carbon fibers of the fiber-reinforced thermoplastic resin molded article measured by (5) and the density (ρc) of the fiber-reinforced thermoplastic resin molded article measured by (6) were determined by the following formula. The volume fraction (Vf) of the carbon fibers of the fiber-reinforced thermoplastic resin molded body, the volume content ratio (Vr) of the thermoplastic resin, and the void ratio (Vv).

Vf＝Wf×ρc/ρf(單位：體積%)Vr＝(100－Wf)×ρc/ρr(單位：體積%)Vv＝100－(Vf＋Vr)(單位：體積%)．ρc：纖維強化熱可塑性樹脂成形體的密度．ρf：碳纖維的密度．ρr：熱可塑性樹脂的密度．Wf：纖維強化熱可塑性樹脂成形體之碳纖維的重量含有率Vf=Wf×ρc/ρf (unit: vol%) Vr=(100-Wf)×ρc/ρr (unit: vol%) Vv=100-(Vf+Vr) (unit: vol%). Ρc: density of fiber-reinforced thermoplastic resin molded body. Ρf: the density of carbon fiber. Ρr: the density of the thermoplastic resin. Wf: weight content of carbon fiber in the fiber-reinforced thermoplastic resin molded body

(8)彎曲特性的測定方法(8) Method for measuring bending characteristics

關於纖維強化熱可塑性樹脂成形體，任意設定1條成為角度基準的基準直線。在相對於基準直線成平行的方向及垂直的方向中，切出各5張(合計10張)寬度15mm×長度80mm之尺寸的試驗片，在60℃的溫度進行24小時的真空乾燥後，在乾燥器內冷卻到室溫為止。於無法採集該尺寸的彎曲特性評價用試驗片時，則製作寬度5mm以上之寬度與長度的比為15/80的試驗片。於試驗片中，廻避纖維強化熱可塑性樹脂成形體的端部，儘可能地使用中央附近之沒有突面、肋條和成形體的厚度變化之部分。Regarding the fiber-reinforced thermoplastic resin molded body, one reference straight line which is an angle reference is arbitrarily set. In a direction parallel to the reference line and in a direction perpendicular to the reference line, a test piece having a size of 15 sheets (a total of 10 sheets) having a width of 15 mm and a length of 80 mm was cut out, and vacuum-dried at a temperature of 60 ° C for 24 hours. Allow to cool to room temperature in the dryer. When the test piece for evaluation of the bending property of this size could not be collected, a test piece having a width of 5 mm or more and a ratio of width to length of 15/80 was produced. In the test piece, the end portion of the fiber-reinforced thermoplastic resin molded body was avoided, and as much as possible, a portion having no thickness, a rib, and a thickness change of the molded body near the center was used.

使用該試驗片，依照ISO178法(1993)，使用3點彎曲試驗夾具(壓頭10mm、支點10mm)，將支點間距離設定為試驗片厚度的16±1倍，以5mm/分鐘的試驗速度來測定彎曲特性。測定數係n＝10，以平均值P當作彎曲強度。又，測定負荷荷重在100~200N的範圍內之彎曲彈性模數，以測定數n＝10的平均值E當作彎曲彈性模數。再者，於本實施例中，使用INSTRON公司製的“INSTRON”(註冊商標)萬能試驗機4201型當作試驗機。Using this test piece, according to the ISO178 method (1993), using a 3-point bending test jig (indenter 10 mm, fulcrum 10 mm), the distance between the fulcrums was set to 16 ± 1 times the thickness of the test piece, and the test speed was 5 mm/min. The bending characteristics were measured. The number of measurements is n=10, and the average value P is taken as the bending strength. Further, the bending elastic modulus of the load load in the range of 100 to 200 N was measured, and the average value E of the measurement number n = 10 was taken as the bending elastic modulus. Further, in the present embodiment, the "INSTRON" (registered trademark) universal testing machine Model 4201 manufactured by INSTRON Co., Ltd. was used as a testing machine.

又，使用測定數n＝10的彎曲強度之平均值P及標準偏差σ，用下式求得彎曲強度的安定性。Moreover, the average value P of the bending strength and the standard deviation σ of the measurement number n=10 were used, and the stability of the bending strength was obtained by the following formula.

．彎曲強度的安定性＝100×σ/P(單位：%). Stability of bending strength = 100 × σ / P (unit: %)

(9)成形材料的操作性(9) Operational properties of forming materials

測定用於製造成形材料的熱可塑性樹脂及碳纖維之合計重量(Wa)。接著，將所得到的成形材料在真空下、80℃的溫度進行24小時的乾燥。測定經乾燥而得的成形材料之重量(Wb)，藉由下式來求得在成形材料的製造步驟中原料脫落的比例(Wc)。The total weight (Wa) of the thermoplastic resin and the carbon fibers used for the production of the molding material was measured. Next, the obtained molding material was dried under vacuum at a temperature of 80 ° C for 24 hours. The weight (Wb) of the dried molding material was measured, and the ratio (Wc) at which the raw material fell off in the production step of the molding material was determined by the following formula.

Wc＝100×(Wa－Wb)/Wa(單位：%)Wc=100×(Wa-Wb)/Wa (unit: %)

作為成形材料之操作性的指標，測定在成形材料的製造步驟中原料的脫落量，藉由以下2個等級來評價。○係合格，×係不合格As an index of the workability of the molding material, the amount of the raw material falling off in the production step of the molding material was measured and evaluated by the following two grades. ○ is qualified, × is unqualified

○：Wc係3%以下。○: Wc is 3% or less.

×：Wc係比3%大。×: Wc is larger than 3%.

下述實施例和比較例中所用的原料係如下。The materials used in the following examples and comparative examples are as follows.

[A1~A3原料][A1~A3 raw materials]

使用由99.4莫耳%的丙烯腈(AN)與0.6莫耳%甲基丙烯酸所成的共聚物，藉由乾濕式紡絲方法以得到單纖維丹尼1d、單絲數12000的丙烯腈系纖維束。將所得到的丙烯腈系纖維束在240~280℃的溫度之空氣中，於1.05的拉伸比下進行加熱，轉換成耐火化纖維，接著在氮氣氛中於300~900℃的溫度範圍，以200℃/分鐘的升溫速度進行10%的拉伸後，升溫到1300℃的溫度為止及培燒。再藉由浸積法給予上漿劑，在120℃的溫度之加熱空氣中使乾燥，而得到PAN系碳纖維。A copolymer of 99.4 mol% acrylonitrile (AN) and 0.6 mol% methacrylic acid was used to obtain a single fiber denier 1 d and a monofilament number 12000 acrylonitrile system by a dry-wet spinning method. Fiber bundles. The obtained acrylic fiber-based fiber bundle is heated in a temperature of 240 to 280 ° C at a draw ratio of 1.05 to be converted into a refractory fiber, and then in a nitrogen atmosphere at a temperature range of 300 to 900 ° C. After stretching at 10% at a temperature elevation rate of 200 ° C /min, the temperature was raised to a temperature of 1300 ° C and calcined. Further, the sizing agent was applied by a dip method, and dried in a heated air at a temperature of 120 ° C to obtain PAN-based carbon fibers.

．A1：PAN系碳纖維總單絲數 12000條單纖維直徑 7μm每單位長度的質 0.8g/m比重 1.8g/cm3 拉伸強度 4.2GPa拉伸彈性模數 230GPa上漿種類 聚氧化乙烯油基醚上漿附著量 1.5重量%. A1: PAN series carbon fiber total filament count 12000 single fiber diameter 7μm per unit length mass 0.8g/m specific gravity 1.8g/cm 3 tensile strength 4.2GPa tensile elastic modulus 230GPa sizing type polyoxyethylene oleyl ether Sizing adhesion amount 1.5% by weight

．A2：PAN系碳纖維總單絲數 12000條單纖維直徑 7μm每單位長度的質量 0.8g/m比重 1.8g/cm3 拉伸強度 4.2GPa拉伸彈性模數 230GPa上漿種類 雙酚A型環氧樹脂上漿附著量 2.0重量%。. A2: PAN carbon fiber total filament count 12000 single fiber diameter 7μm mass per unit length 0.8g/m specific gravity 1.8g/cm 3 tensile strength 4.2GPa tensile elastic modulus 230GPa sizing type bisphenol A epoxy The resin sizing adhesion amount was 2.0% by weight.

[B1~B3原料][B1~B3 raw materials]

．B1：耐隆6樹脂東麗(股)製，“東麗AMILAN”(註冊商標)CM1001比重 1.13熔點 210℃. B1: Nylon 6 resin Toray (share) system, "Dongli AMILAN" (registered trademark) CM1001 specific gravity 1.13 melting point 210 ° C

．B2：馬來酸酐改性聚丙烯樹脂三井化學(股)製，“ADMER”(註冊商標)QE510比重 0.91熔點 160℃. B2: Maleic anhydride modified polypropylene resin Mitsui Chemicals Co., Ltd., "ADMER" (registered trademark) QE510 specific gravity 0.91 melting point 160 °C

．B3：聚對酞酸丁二酯樹脂東麗(股)製，“TORAYCON”(註冊商標)1200S比重 1.31熔點 225℃. B3: Polybutylene terephthalate resin Toray (share) system, "TORAYCON" (registered trademark) 1200S specific gravity 1.31 melting point 225 ° C

(實施例1)(Example 1)

藉由筒形刀具將A1(碳纖維)切割成6.4mm，以得到短切碳纖維(A1－1)。藉由筒形刀具將B1(耐隆6樹脂)的纖維(單纖維纖度3dtex)切割成5.0mm，以得到短切樹脂纖維(B1－1)。A1 (carbon fiber) was cut into 6.4 mm by a cylindrical cutter to obtain chopped carbon fibers (A1-1). B1 (Nylon 6 resin) fiber (single fiber fineness 3dtex) was cut into 5.0 mm by a cylindrical cutter to obtain a chopped resin fiber (B1-1).

製作200升由水與界面活性劑(NACALAI科技(股)製，聚氧化乙烯月桂基醚(商品名))所成之濃度0.1重量%的分散液，於該分散液中，投入107克A1－1(短切碳纖維)和153克B1－1(短切樹脂纖維)，攪拌10分鐘後，流入具有長度400mm×寬度400mm之造紙面的大型四角型片製造機(熊谷理機工業株式會社製，NO.2553－I(商品名))，吸氣、脫泡，以得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係41重量%。200 liters of a dispersion of 0.1% by weight of water and a surfactant (manufactured by NACALAI Technologies, polyoxyethylene lauryl ether (trade name)) was prepared, and 107 g of A1- was added to the dispersion. 1 (short-cut carbon fiber) and 153 g of B1-1 (short-cut resin fiber), and the mixture was stirred for 10 minutes, and then flowed into a large-sized four-corner sheet making machine (manufactured by Kumagai Riki Kogyo Co., Ltd.) having a length of 400 mm × a width of 400 mm. NO.2553-I (trade name)), inhaled and defoamed to obtain a molding material having a length of 400 mm and a width of 400 mm. The weight content of the carbon fibers was 41% by weight.

將所得到的成形材料在真空下、80℃的溫度下乾燥24小時。藉由遠紅外線加熱爐，在氮氣氛下，將2片成形材料預熱到280℃，於模腔表面溫度150℃之具有厚度1.6mm、縱400mm×橫400mm的平板狀模腔之模具中將經預熱的2片成形材料以積層的狀態作配置(裝料率100%)，關閉模具，在成形壓力30MPa下作加壓。於成形壓力達到30MPa的2秒後，去除成形壓力，除壓結束後立刻再以30MPa的成形壓力作加壓，進行此操作2次，以去除成形材料中所含有的空氣。接著，於30MPa的加壓下，保持2分鐘後，打開模具、脫模，而得到纖維強化熱可塑性樹脂成形體。The obtained molding material was dried under vacuum at a temperature of 80 ° C for 24 hours. The two forming materials were preheated to 280 ° C in a nitrogen atmosphere by a far-infrared heating furnace, and a mold having a flat cavity of 1.6 mm in thickness, 400 mm in length × 400 mm in width was applied to a cavity surface temperature of 150 ° C. The two pre-heated molding materials were placed in a laminated state (loading rate: 100%), the mold was closed, and the molding was performed at a molding pressure of 30 MPa. After 2 seconds from the molding pressure of 30 MPa, the molding pressure was removed, and immediately after the completion of the pressure, the molding pressure was applied at a molding pressure of 30 MPa, and this operation was performed twice to remove the air contained in the molding material. Subsequently, after holding for 2 minutes under a pressure of 30 MPa, the mold was opened and demolded to obtain a fiber-reinforced thermoplastic resin molded body.

(實施例2)(Example 2)

除了將139克A1－1(短切碳纖維)和133克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係51重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 139 g of A1-1 (chopped carbon fiber) and 133 g of B1-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 51% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

第3圖係顯示本發明的實施例2所得到的纖維強化熱可塑性樹脂成形體之縱剖面的光學顯微鏡照片。Fig. 3 is an optical micrograph showing a longitudinal section of a fiber-reinforced thermoplastic resin molded article obtained in Example 2 of the present invention.

(實施例3)(Example 3)

除了將193克A1－1(短切碳纖維)和99克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係66重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 193 g of A1-1 (chopped carbon fiber) and 99 g of B1-1 (short-cut resin fiber) were put into the dispersion. . The carbon fiber had a weight content of 66% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(實施例4)(Example 4)

藉由筒形刀具將A1(碳纖維)切割成2.0mm，以得到短切碳纖維(A1－2)。除了將139克A1－2(短切碳纖維)和133克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係51重量%。A1 (carbon fiber) was cut into 2.0 mm by a cylindrical cutter to obtain chopped carbon fibers (A1-2). A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 139 g of A1-2 (chopped carbon fiber) and 133 g of B1-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 51% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(實施例5)(Example 5)

藉由筒形刀具將A1(碳纖維)切割成12.7mm，以得到短切碳纖維(A1－3)。除了將70克A1－3(短切碳纖維)和67克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係51重量%。A1 (carbon fiber) was cut into 12.7 mm by a cylindrical cutter to obtain chopped carbon fibers (A1-3). A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 70 g of A1-3 (chopped carbon fiber) and 67 g of B1-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 51% by weight.

藉由遠紅外線加熱爐，在氮氣氛下，將4片成形材料預熱到280℃，於具有平板狀模腔的模具中將經預熱的4片成形材料以積層的狀態作配置，以外係藉由實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。4 pieces of the forming material were preheated to 280 ° C in a nitrogen atmosphere by a far-infrared heating furnace, and the pre-heated four forming materials were placed in a laminated state in a mold having a flat cavity. A fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(實施例6)(Example 6)

藉由筒形刀具將B1(耐隆6樹脂)的纖維(單纖維纖度3dtex)切割成3.0mm，以得到短切樹脂纖維(B1－2)。將139克A1－1(短切碳纖維)和133克B1－2(短切樹脂纖維)投入分散容器內。此處的分散容器係使用底面直徑600mm、高度600mm的圓柱形狀，內容積為200升，具有從側面朝向底面中心部將高速空氣導入的空氣吹入口，上面具有經由過濾器將空氣排出的空氣排出口，具有可取出所投入原料之可脫附的底面之容器。於分散容器內導入高速空氣，將A1－1(短切碳纖維)和B1－2(短切樹脂纖維)開鬆，混合10分鐘。混合後，停止空氣的導入，使A1－1(短切碳纖維)與B1－2(短切樹脂纖維)的混合物堆積在分散容器的底面。拆下分散容器的底面，切割成長度400mm、寬度400mm，得到成形材料。碳纖維的重量含有率係51重量%。B1 (Nylon 6 resin) fiber (single fiber fineness 3dtex) was cut into 3.0 mm by a cylindrical cutter to obtain chopped resin fiber (B1-2). 139 g of A1-1 (chopped carbon fiber) and 133 g of B1-2 (chopped resin fiber) were placed in a dispersion vessel. The dispersion container here has a cylindrical shape having a bottom surface diameter of 600 mm and a height of 600 mm and an internal volume of 200 liters, and has an air inlet port for introducing high-speed air from the side surface toward the center portion of the bottom surface, and an air row for discharging air through the filter. The outlet has a container that can take out the detachable bottom surface of the input material. High-speed air was introduced into the dispersion vessel, and A1-1 (chopped carbon fiber) and B1-2 (short-cut resin fiber) were opened and mixed for 10 minutes. After the mixing, the introduction of air was stopped, and a mixture of A1-1 (chopped carbon fiber) and B1-2 (short-cut resin fiber) was deposited on the bottom surface of the dispersion container. The bottom surface of the dispersion container was removed, and cut into a length of 400 mm and a width of 400 mm to obtain a molding material. The weight content of the carbon fibers was 51% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(比較例1)(Comparative Example 1)

使用JSW製TEX．30α型二軸擠壓機(螺桿直徑30mm,機筒溫度270℃,轉數150rpm)，充分乾燥以使得A1－1(短切碳纖維)的水分率成為0.05%以下後，從副料斗將其投入，及從主料斗將B1(耐隆6樹脂)投入，將它們充分捏合，通過擠片模頭連續地擠壓出厚度0.8mm、寬度300mm的基材，冷卻後，藉由刀具裁斷成長度1000mm，得到碳纖維的重量含有率為41重量%的成形材料。Use JSW to make TEX. 30α type two-axis extruder (screw diameter 30mm, barrel temperature 270 ° C, number of revolutions 150 rpm), fully dried so that the moisture content of A1-1 (short-cut carbon fiber) becomes 0.05% or less, and then it is put into the sub hopper And B1 (Nylon 6 resin) is put in from the main hopper, and they are fully kneaded, and the substrate having a thickness of 0.8 mm and a width of 300 mm is continuously extruded through the extrusion die, and after cooling, it is cut into a length of 1000 mm by a cutter. A molded material having a carbon fiber weight content of 41% by weight was obtained.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(比較例2)(Comparative Example 2)

藉由筒形刀具將A2(碳纖維)切割成6.4mm，以得到短切碳纖維(A2－1)。除了將174克A2－1(短切碳纖維)和111克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係61重量%。A2 (carbon fiber) was cut into 6.4 mm by a cylindrical cutter to obtain chopped carbon fibers (A2-1). A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 174 g of A2-1 (chopped carbon fiber) and 111 g of B1-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 61% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。第4圖係顯示比較例2所得到的纖維強化熱可塑性樹脂成形體之縱剖面的光學顯微鏡照片。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1. Fig. 4 is an optical micrograph showing a longitudinal section of the fiber-reinforced thermoplastic resin molded article obtained in Comparative Example 2.

(比較例3)(Comparative Example 3)

將比較例1所得到的成形材料切割成長度7mm、寬度7mm，在真空下、80℃乾燥24小時後，使用螺桿形狀為全螺線形狀的日本製鋼所(股)製J350EIII，在螺桿轉數60rpm、料筒溫度280℃、射出速度90mm/sec、射出壓力200MPa、背壓0.5MP a、模具溫度55℃下，得到厚度1.6mm、縱200mm×橫200mm的平板狀纖維強化熱可塑性樹脂成形體。碳纖維的重量含有率係41重量%。The molding material obtained in Comparative Example 1 was cut into a length of 7 mm and a width of 7 mm, and dried under vacuum at 80 ° C for 24 hours, and then J350EIII manufactured by Nippon Steel Works Co., Ltd. having a screw shape of a full spiral shape was used. 60 rpm, a cylinder temperature of 280 ° C, an injection speed of 90 mm/sec, an injection pressure of 200 MPa, a back pressure of 0.5 MP a, and a mold temperature of 55 ° C, a flat fiber-reinforced thermoplastic resin molded body having a thickness of 1.6 mm and a length of 200 mm × a width of 200 mm was obtained. . The weight content of the carbon fibers was 41% by weight.

(比較例4)(Comparative Example 4)

除了將70克A1－1(短切碳纖維)和176克B1－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係28重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 70 g of A1-1 (chopped carbon fiber) and 176 g of B1-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 28% by weight.

又，藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 1.

(比較例5)(Comparative Example 5)

將B1(耐隆6樹脂)的丸粒冷凍粉碎後，藉由14網目(開孔徑1.18mm)的篩子來分級所得到粉碎粒子，再藉由60網目(開孔徑0.25mm)的篩子來分級已通過14網目的篩子之粉碎粒子，採集60網目的篩子上所殘留的粉碎粒子，得到14~60網目的樹脂粒子(B1－2)。除了將139克A1－1(短切碳纖維)和133克B1－2(樹脂粒子)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率，由於成形材料中樹脂粒子脫落，故成為56重量%。After freeze-pulverizing the pellets of B1 (Nylon 6 resin), the pulverized particles were classified by a sieve of 14 mesh (opening aperture 1.18 mm), and classified by a sieve of 60 mesh (opening aperture 0.25 mm). The pulverized particles remaining on the sieve of 60 mesh were collected by the pulverized particles of the sieve of 14 mesh to obtain resin particles (B1-2) of 14 to 60 mesh. A molding material having a length of 400 mm and a width of 400 mm was obtained in the same manner as in Example 1 except that 139 g of A1-1 (chopper carbon fiber) and 133 g of B1-2 (resin particles) were placed in the dispersion. The weight content of the carbon fibers was 56% by weight because the resin particles in the molding material fell off.

(實施例7)(Example 7)

藉由筒形刀具將B2(馬來酸酐改性聚丙烯樹脂)的纖維(單纖維纖度3dtex)切割成5.0mm，以得到短切樹脂纖維(B2－1)。除了將140克A1－1(短切碳纖維)和106克B2－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係57重量%。The fiber of B2 (maleic anhydride-modified polypropylene resin) (single fiber fineness 3dtex) was cut into 5.0 mm by a cylindrical cutter to obtain a chopped resin fiber (B2-1). A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 140 g of A1-1 (chopped carbon fiber) and 106 g of B2-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 57% by weight.

將所得的成形材料在真空下、60℃的溫度進行24小時的乾燥。藉由遠紅外線加熱爐，在氮氣氛下，將2片成形材料預熱到210℃，於模腔表面溫度100℃之具有厚度1.6mm、縱400mm×橫400mm的平板狀模腔之模具中將經預熱的2片成形材料以積層的狀態作配置，以外係藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。The obtained molding material was dried under vacuum at a temperature of 60 ° C for 24 hours. The two forming materials were preheated to 210 ° C under a nitrogen atmosphere by a far-infrared heating furnace, and a mold having a flat cavity of 1.6 mm in thickness, 400 mm in length × 400 mm in width was applied to a cavity surface temperature of 100 ° C. The two pre-heated two molding materials were placed in a laminated state, and a fiber-reinforced thermoplastic resin molded body was obtained in the same manner as in Example 1.

(實施例8)(Example 8)

除了將193克A1－1(短切碳纖維)和80克B2－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係71重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 193 g of A1-1 (chopped carbon fiber) and 80 g of B2-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 71% by weight.

又，藉由與實施例7同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 7.

(實施例9)(Example 9)

藉由筒形刀具將B3(聚對酞酸丁二酯樹脂)的纖維(單纖維纖度3dtex)切割成5.0mm，以得到短切樹脂纖維(B3－1)。除了將105克A1－1(短切碳纖維)和179克B3－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係37重量%。The fiber of B3 (polybutylene terephthalate resin) (single fiber fineness 3dtex) was cut into 5.0 mm by a cylindrical cutter to obtain a chopped resin fiber (B3-1). A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 105 g of A1-1 (chopped carbon fiber) and 179 g of B3-1 (short-cut resin fiber) were put into the dispersion. . The weight content of the carbon fibers was 37% by weight.

將所得到的成形材料在真空下、130℃的溫度進行24小時乾燥。藉由遠紅外線加熱爐，在氮氣氛下，將2片成形材料預熱到270℃，於模腔表面溫度130℃之具有厚度1.6mm、縱400mm×橫400mm的平板狀模腔之模具中將經預熱的2片成形材料以積層的狀態作配置，以外係藉由與實施例1同樣的方法，得到纖維強化熱可塑性樹脂成形體。The obtained molding material was dried under vacuum at a temperature of 130 ° C for 24 hours. The two forming materials were preheated to 270 ° C in a nitrogen atmosphere by a far-infrared heating furnace, and a mold having a flat cavity of 1.6 mm in thickness, 400 mm in length × 400 mm in width was applied to a cavity surface temperature of 130 ° C. The two pre-heated two molding materials were placed in a laminated state, and a fiber-reinforced thermoplastic resin molded body was obtained in the same manner as in Example 1.

(實施例10)(Embodiment 10)

除了將140克A1－1(短切碳纖維)和153克B3－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係48重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 140 g of A1-1 (chopped carbon fiber) and 153 g of B3-1 (short-cut resin fiber) were placed in the dispersion. . The weight content of the carbon fibers was 48% by weight.

又，藉由與實施例9同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 9.

(比較例6)(Comparative Example 6)

除了將246克A1－1(短切碳纖維)和53克B2－1(短切樹脂纖維)投入分散液中以外，係藉由與實施例1同樣的方法，得到長度400mm、寬度400mm的成形材料。碳纖維的重量含有率係82重量%。A molding material having a length of 400 mm and a width of 400 mm was obtained by the same method as in Example 1 except that 246 g of A1-1 (chopped carbon fiber) and 53 g of B2-1 (short-cut resin fiber) were put into the dispersion. . The weight content of the carbon fibers was 82% by weight.

又，藉由與實施例7同樣的方法，得到纖維強化熱可塑性樹脂成形體。Further, a fiber-reinforced thermoplastic resin molded article was obtained in the same manner as in Example 7.

表1中彙總上述實施例1~6和比較例1~4的纖維強化熱可塑性樹脂成形體，表2中彙總實施例1~6和比較例1、2、4、5的成形材料之評價結果。The fiber-reinforced thermoplastic resin molded articles of the above Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1, and the evaluation results of the molding materials of Examples 1 to 6 and Comparative Examples 1, 2, 4, and 5 are summarized in Table 2. .

由表1中所示的實施例1~6和比較例1~4之結果，可明瞭以下者。即，實施例1的纖維強化熱可塑性樹脂成形體，當與比較例1的纖維強化熱可塑性樹脂成形體比較下，係力學特性優異。實施例1的纖維強化熱可塑性樹脂成形體，當與比較例3的纖維強化熱可塑性樹脂成形體比較下，係各向同性優異。又，實施例1、2、3的纖維強化熱可塑性樹脂成形體，當與比較例2的纖維強化熱可塑性樹脂成形體比較下，係力學特性優異。又，實施例1、2、3、4、5、6的纖維強化熱可塑性樹脂成形體，當與比較例4的纖維強化熱可塑性樹脂成形體比較下，係各向同性優異。From the results of Examples 1 to 6 and Comparative Examples 1 to 4 shown in Table 1, the following can be clarified. In other words, the fiber-reinforced thermoplastic resin molded article of Example 1 was excellent in mechanical properties as compared with the fiber-reinforced thermoplastic resin molded article of Comparative Example 1. The fiber-reinforced thermoplastic resin molded article of Example 1 was excellent in isotropy as compared with the fiber-reinforced thermoplastic resin molded article of Comparative Example 3. Further, the fiber-reinforced thermoplastic resin molded articles of Examples 1, 2, and 3 were excellent in mechanical properties as compared with the fiber-reinforced thermoplastic resin molded article of Comparative Example 2. Further, the fiber-reinforced thermoplastic resin molded articles of Examples 1, 2, 3, 4, 5, and 6 were excellent in isotropy as compared with the fiber-reinforced thermoplastic resin molded article of Comparative Example 4.

由表2中所示的實施例1~6和比較例1、2、4、5的結果，可明瞭以下者。即，實施例1、2、3、4、5、6的成形材料，當與比較例1、4比較下，係各向同性優異。又，實施例1、2、3的成形材料，當與比較例2、5比較下，係成形材料的操作性優異。From the results of Examples 1 to 6 and Comparative Examples 1, 2, 4, and 5 shown in Table 2, the following can be clarified. That is, the molding materials of Examples 1, 2, 3, 4, 5, and 6 were excellent in isotropy when compared with Comparative Examples 1 and 4. Further, in the molding materials of Examples 1, 2, and 3, the molding materials were excellent in workability in comparison with Comparative Examples 2 and 5.

表3中彙總上述實施例7~10和比較例6的纖維強化熱可塑性樹脂成形體之評價結果，表4中彙總上述實施例7~10和比較例6的成形材料之評價結果。Table 3 summarizes the evaluation results of the fiber-reinforced thermoplastic resin molded articles of the above Examples 7 to 10 and Comparative Example 6, and Table 4 summarizes the evaluation results of the molding materials of the above Examples 7 to 10 and Comparative Example 6.

由表3中所示的實施例7~10和比較例6的結果，可明瞭以下者。即，實施例7、8的纖維強化熱可塑性樹脂成形體，當與比較例6的纖維強化熱可塑性樹脂成形體比較下，係力學特性優異。又，實施例7~10的纖維強化熱可塑性樹脂成形體，在各種各樣的熱可塑性樹脂中，顯示能得到高的力學特性。From the results of Examples 7 to 10 and Comparative Example 6 shown in Table 3, the following can be clarified. In other words, the fiber-reinforced thermoplastic resin molded articles of Examples 7 and 8 were excellent in mechanical properties as compared with the fiber-reinforced thermoplastic resin molded article of Comparative Example 6. Further, the fiber-reinforced thermoplastic resin molded articles of Examples 7 to 10 exhibited high mechanical properties in various thermoplastic resins.

由表4中所示的實施例7~10和比較例6之結果，可明瞭以下者。即，實施例7、8的成形材料，當與比較例6的成形材料比較下，係操作性優異。又，實施例7~10的成形材料，在各種各樣的熱可塑性樹脂和碳纖維中，顯示能得到各向同性且操作性優異的成形材料。From the results of Examples 7 to 10 and Comparative Example 6 shown in Table 4, the following can be clarified. In other words, the molding materials of Examples 7 and 8 were excellent in workability in comparison with the molding material of Comparative Example 6. Further, in the molding materials of Examples 7 to 10, various types of thermoplastic resins and carbon fibers were used to exhibit a molding material which was excellent in isotropic properties and excellent in handleability.

產業上的利用可能性Industrial utilization possibility

本發明的纖維強化熱可塑性樹脂成形體，由於以高含有率含有單纖維狀的碳纖維，其纖維長度長，且碳纖維被任意地配置，故可成為力學特性優異、更具有各向同性的力學特性之纖維強化熱可塑性樹脂成形體，適用於電氣．電子機器、OA機器、家電機器、土木．建築、汽車、航空器的零件、構造零件及殼體等。Since the fiber-reinforced thermoplastic resin molded article of the present invention contains a single-fiber carbon fiber at a high content, the fiber length is long and the carbon fibers are arbitrarily arranged, so that mechanical properties are excellent and isotropic properties are obtained. Fiber-reinforced thermoplastic resin molded body, suitable for electrical. Electronic equipment, OA machines, home appliances, civil engineering. Construction, automotive, aircraft parts, structural parts and housings.

本發明的成形材料，因為係由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，故操作性優良，而且因為以高含有率含有碳纖維，其纖維長度長，且碳纖維被任意地配置，故適用於力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體之成形。Since the molding material of the present invention is composed of a single-fiber carbon fiber and a single-fiber thermoplastic resin fiber, it has excellent handleability, and since it contains carbon fibers at a high content rate, the fiber length is long, and the carbon fibers are arbitrarily Since it is disposed, it is suitable for the formation of a fiber-reinforced thermoplastic resin molded body excellent in mechanical properties and isotropy.

本發明的製造方法係藉由將上述成形材料壓縮成形，而適用於製造力學特性及其各向同性優異的纖維強化熱可塑性樹脂成形體。The production method of the present invention is suitable for producing a fiber-reinforced thermoplastic resin molded article excellent in mechanical properties and isotropy by compression-molding the above-mentioned molding material.

本說明書中所引用的全部刊物、發明專利及發明專利申請案係照原樣地作參考，而納入本說明書中。All publications, invention patents, and invention patent applications cited in this specification are hereby incorporated by reference in their entirety in their entirety.

1．．．碳纖維1. . . carbon fiber

2．．．熱可塑性樹脂2. . . Thermoplastic resin

第1圖係碳纖維以單纖維的狀態分散在熱可塑性樹脂中的纖維強化熱可塑性樹脂成形體之剖面示意圖。Fig. 1 is a schematic cross-sectional view showing a fiber-reinforced thermoplastic resin molded body in which carbon fibers are dispersed in a thermoplastic resin in a state of a single fiber.

第2圖係碳纖維以束狀態存在的纖維強化熱可塑性樹脂成形體之剖面示意圖。Fig. 2 is a schematic cross-sectional view showing a fiber-reinforced thermoplastic resin molded body in which carbon fibers are present in a bundle state.

第3圖係顯示本發明的實施例2所得到纖維強化熱可塑性樹脂成形體之剖面的光學顯微鏡照片。Fig. 3 is an optical micrograph showing a cross section of a fiber-reinforced thermoplastic resin molded article obtained in Example 2 of the present invention.

第4圖係顯示比較例2所得到的纖維強化熱可塑性樹脂成形體之剖面的光學顯微鏡照片。Fig. 4 is an optical micrograph showing a cross section of the fiber-reinforced thermoplastic resin molded body obtained in Comparative Example 2.

Claims (18)

一種纖維強化熱可塑性樹脂成形體，其係由20~65重量%的熱可塑性樹脂與35~80重量%的碳纖維所成的成形體，該碳纖維係單纖維狀，而且該碳纖維的重量平均纖維長度(Lw)係在0.5~10mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在-0.25~0.25的範圍。 A fiber-reinforced thermoplastic resin molded body comprising 20 to 65% by weight of a thermoplastic resin and 35 to 80% by weight of carbon fibers, the carbon fiber being monofibrous, and the weight average fiber length of the carbon fiber (Lw) is in the range of 0.5 to 10 mm, and the alignment parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25. 如申請專利範圍第1項之纖維強化熱可塑性樹脂成形體，其中上述碳纖維之本說明書中所定義的分散參數係在0~25%的範圍。 The fiber-reinforced thermoplastic resin molded article according to claim 1, wherein the dispersion parameter defined in the specification of the carbon fiber is in the range of 0 to 25%. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成形體，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最大值係0.29以下。 The fiber-reinforced thermoplastic resin molded article according to claim 1 or 2, wherein a maximum value of the relative degree of the 30° mark defined in the present specification is 0.29 or less in the distribution angle degree distribution of the carbon fiber. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成形體，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最小值係0.03以上。 The fiber-reinforced thermoplastic resin molded article according to claim 1 or 2, wherein a minimum value of the relative degree of the 30° mark defined in the present specification is 0.03 or more in the distribution angle degree distribution of the carbon fiber. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成形體，其中上述碳纖維的纖維長度1.0mm以上的碳纖維條數係為總碳纖維條數的30~100%之範圍。 The fiber-reinforced thermoplastic resin molded article according to claim 1 or 2, wherein the carbon fiber has a fiber length of 1.0 mm or more and a number of carbon fibers of 30 to 100% of the total number of carbon fibers. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成 形體，其中上述纖維強化熱可塑性樹脂成形體之本說明書中所定義的空隙率係5%以下。 Fiber reinforced thermoplastic resin as claimed in claim 1 or 2 In the form of the fiber-reinforced thermoplastic resin molded article, the void ratio defined in the present specification is 5% or less. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成形體，其中上述纖維強化熱可塑性樹脂成形體之根據ISO178的彎曲強度係在350~1100MPa的範圍。 The fiber-reinforced thermoplastic resin molded article according to claim 1 or 2, wherein the fiber-reinforced thermoplastic resin molded article has a flexural strength according to ISO178 of 350 to 1100 MPa. 如申請專利範圍第1或2項之纖維強化熱可塑性樹脂成形體，其中於上述纖維強化熱可塑性樹脂成形體之根據ISO178的彎曲強度中，彎曲強度的安定性係10%以下。 The fiber-reinforced thermoplastic resin molded article according to the first or second aspect of the invention, wherein the flexural strength according to ISO178 of the fiber-reinforced thermoplastic resin molded article is 10% or less. 一種成形材料，其係為由20~65重量%的熱可塑性樹脂纖維與35~80重量%的碳纖維所構成的成形材料，由單纖維狀的碳纖維與單纖維狀的熱可塑性樹脂纖維所構成，該碳纖維的重量平均纖維長度(Lw)係在1~15mm的範圍，本說明書中所定義的該碳纖維之配向參數(fp)係在-0.25~0.25的範圍。 A molding material comprising 20 to 65% by weight of a thermoplastic resin fiber and 35 to 80% by weight of carbon fiber, and is composed of a single fiber carbon fiber and a single fiber thermoplastic resin fiber. The weight average fiber length (Lw) of the carbon fiber is in the range of 1 to 15 mm, and the orientation parameter (fp) of the carbon fiber defined in the present specification is in the range of -0.25 to 0.25. 如申請專利範圍第9項之成形材料，其中上述單纖維狀的熱可塑性樹脂纖維係與至少2條以上的上述單纖維狀的碳纖維相接。 The molding material according to claim 9, wherein the single-fiber thermoplastic resin fiber is in contact with at least two or more of the above-mentioned single-fiber carbon fibers. 如申請專利範圍第9或10項之成形材料，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最大值係0.29以下。 The molding material according to claim 9 or 10, wherein in the distribution angle degree distribution of the carbon fibers, the maximum value of the relative degree of the 30° engraving defined in the present specification is 0.29 or less. 如申請專利範圍第9或10項之成形材料，其中於上述碳纖維的配向角度度數分布中，本說明書中所定義的30°刻紋的相對度數之最小值係0.03以上。 The molding material according to claim 9 or 10, wherein the minimum degree of the relative degree of the 30° mark defined in the present specification is 0.03 or more in the distribution angle degree distribution of the carbon fiber. 如申請專利範圍第9或10項之成形材料，其中上述碳纖維之本說明書中所定義的分散參數係在0~25%的範圍。 The molding material according to claim 9 or 10, wherein the dispersion parameter defined in the specification of the carbon fiber is in the range of 0 to 25%. 如申請專利範圍第9或10項之成形材料，其中上述碳纖維的重量平均纖維長度(Lw)與數平均纖維長度(Ln)的比(Lw/Ln)係在1.0~2.5的範圍。 The molding material according to claim 9 or 10, wherein a ratio (Lw/Ln) of the weight average fiber length (Lw) to the number average fiber length (Ln) of the carbon fibers is in the range of 1.0 to 2.5. 一種纖維強化熱可塑性樹脂成形體之製法，其係將如申請專利範圍第9至14項中任一項之成形材料，以含有至少以下(I)~(V)之步驟的壓縮成形法來成形：(I)將成形材料所含有的熱可塑性樹脂加熱熔融之步驟，(Ⅱ)將成形材料配置於模具中之步驟，(Ⅲ)以模具來加壓成形材料之步驟，(Ⅳ)在模具內將成形材料固化之步驟，(V)打開模具，將纖維強化熱可塑性樹脂成形體脫模之步驟。 A method for producing a fiber-reinforced thermoplastic resin molded article, which is formed by a compression molding method comprising at least the following steps (I) to (V), wherein the molding material according to any one of claims 9 to 14 is formed. (I) a step of heating and melting the thermoplastic resin contained in the molding material, (II) a step of disposing the molding material in the mold, (III) a step of pressing the molding material by the mold, and (IV) a step in the mold. The step of curing the shaped material, (V) the step of opening the mold to demold the fiber-reinforced thermoplastic resin molded body. 如申請專利範圍第15項之纖維強化熱可塑性樹脂成形體之製法，其中於(Ⅲ)的步驟中，進行至少1次以上的去除對成形材料的加壓，再度將成形材料加壓的操作。 The method for producing a fiber-reinforced thermoplastic resin molded article according to claim 15, wherein in the step (III), at least one or more times of removing the pressure of the molding material and pressurizing the molding material are performed. 如申請專利範圍第15或16項之纖維強化熱可塑性樹脂成形體之製法，其中上述壓縮成形的加壓力係2~40MPa。 The method for producing a fiber-reinforced thermoplastic resin molded article according to claim 15 or 16, wherein the compression forming pressure is 2 to 40 MPa. 如申請專利範圍第15或16項之纖維強化熱可塑性樹脂成形體之製法，其中配置於模具的模腔內之成形材料 的裝料率係80%以上。 The method for producing a fiber-reinforced thermoplastic resin molded body according to claim 15 or 16, wherein the molding material is disposed in a cavity of the mold The loading rate is more than 80%.
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